Ion conductive copolymers containing one or more hydrophobic oligomers

ABSTRACT

In one aspect, the invention provides ion conductive copolymers comprising (1) a plurality of first oligomers, (2) a plurality of second oligomers, (3) ion conductive monomers and (4) linking monomers. The oligomers preferably are hydrophobic and together with the ion conductive monomers are randomly dispersed between the linking monomers. Uses of such polymeric materials include the formation of polymer electrolyte membranes (PEMs), catalyst coated membranes (CCM&#39;s) and membrane electrolyte assemblies (MEA&#39;s) which may be used in fuel cells and the like.

TECHNICAL FIELD

This invention relates to ion conductive polymers which are useful informing polymer electrolyte membranes used in fuel cells.

BACKGROUND OF THE INVENTION

Fuel cells have been projected as promising power sources for portableelectronic devices, electric vehicles, and other applications due mainlyto their non-polluting nature. Of various fuel cell systems, the polymerelectrolyte membrane based fuel cell technology such as direct methanolfuel cells (DMFCs) have attracted much interest thanks to their highpower density and high energy conversion efficiency. The “heart” of apolymer electrolyte membrane based fuel cell is the so called“membrane-electrode assembly” (MEA), which comprises a proton exchangemembrane (PEM), catalyst disposed on the opposite surfaces of the PEM toform a catalyst coated membrane (CCM) and a pair of electrodes (i.e., ananode and a cathode) disposed to be in electrical contact with thecatalyst layer.

Proton-conducting membranes for DMFCs are known, such as Nafion® fromthe E.I. Dupont De Nemours and Company or analogous products from DowChemicals. These perfluorinated hydrocarbon sulfonate ionomer products,however, have serious limitations when used in high temperature fuelcell application Nafion® loses conductivity when the operationtemperature of the fuel cell is over 80° C. Moreover, Nafion® has a veryhigh methanol crossover rate, which impedes its applications in DMFCs.

U.S. Pat. No. 5,773,480, assigned to Ballard Power System, describes apartially fluorinated proton conducting membrane fromα,β,β-trifluorostyrene. One disadvantage of this membrane is its highcost of manufacturing due to the complex synthetic processes for monomerα,β,β-trifluorostyrene and the poor sulfonation ability of poly(α,β,β-trifluorostyrene). Another disadvantage of this membrane is thatit is very brittle, thus has to be incorporated into a supportingmatrix.

U.S. Pat. Nos. 6,300,381 and 6,194,474 to Kerrres, et al. describe anacid-base binary polymer blend system for proton conducting membranes,wherein the sulfonated poly(ether sulfone) was made by post-sulfonationof the poly (ether sulfone).

M. Ueda in the Journal of Polymer Science, 31 (1993): 853, discloses theuse of sulfonated monomers to prepare sulfonated poly(ether sulfonepolymers).

U.S. Patent Application US 2002/0091225A1 to McGrath, et al. used thismethod to prepare sulfonated polysulfone polymers.

The need for a good membrane for fuel cell operation requires balancingof various properties of the membrane. Such properties included protonconductivity, fuel-resistance, chemical stability and fuel crossoverespecially for high temperature applications, fast start up of DMFCs,and durability of cell performance. In addition, it is important for themembrane to retain its dimensional stability over the fuel operationaltemperature range. If the membrane swells significantly, it willincrease fuel crossover, resulting in degradation of cell performance.Dimensional changes of the membrane also put stress on the bonding ofthe catalyst membrane-electrode assembly (MEA). Often this results indelamination of the membrane from the catalyst and/or electrode afterexcessive swelling of the membrane. Therefore, it is necessary tomaintain the dimensional stability of the membrane over a widetemperature range and minimize membrane swelling.

SUMMARY OF THE INVENTION

The invention provides ion conductive copolymers which can be used tofabricate proton exchange membranes (PEM's), catalyst coated protonexchange membranes (CCM's) and membrane electrode assemblies (MEA's)which are useful in fuel cells and their application in electronicdevices, power sources and vehicles.

In one aspect, the ion conductive copolymers comprise at least onehydrophobic oligomer (sometimes referred to as segments or blockpolymers) that is randomly dispersed in a polymeric backbone comprisingone or more ion conducting monomers. In another aspect, the ionconductive polymer comprises at least two different hydrophobic monomersrandomly dispensed in the polymer backbone. In a preferred embodiment, alinking monomer is used to link the oligomer and ion conducting monomer.

If two hydrophobic oligomers are used, the first oligomer preferablycomprises a first monomer and a second monomer whereas the secondoligomer comprises third and fourth monomers. In one aspect, theoligomers are hydrophobic. In another aspect, one of the first or secondoligomer is a hard polymer relative to the other.

The ion conductive monomers comprise a monomer and an ion conductivegroup such as a sulfonic acid group. In some embodiments, the samemonomer that does not contain an ion conductive group can be used as thelinking monomer in combination with the ion conductive monomer tocontrol the degree to which the copolymer contains ion conductivegroups. Alternatively, the linking monomer is structurally distinct,i.e., different from the ion conducting monomer. The relative amounts ofmonomers and oligomers used to synthesize the copolymer can be varied tocontrol the relative amount of ion conductive groups in the copolymer.

Prior to synthesis, each of the first oligomer, second oligomer and ionconductive monomer contain leaving groups, such as halides, at theirdistal ends. The linking monomer, on the other hand, comprises twodisplacement groups such as phenoxide, alkoxide or sulfide associatedwith aromatic monomers. Upon reaction of the linking monomer with eachof the first oligomer, second oligomer and ion conductive monomer, thedisplacement groups and the leaving groups react to form a plurality ofdifferent motifs within the ion conductive polymer. Alternatively, thefirst oligomer, second oligomer and ion conducting monomer comprisedisplacement groups and the linking monomer comprises leaving groups.

A first hydrophobic oligomer can be represented by the formula (AB)_(m)Aor (BA)_(m)B. A second hydrophobic oligomer can be represented by theformula (CD)_(n)C or (DC)_(n)D. Each of these oligomers are randomlydistributed in an ion conductive polymer backbone to form a copolymerthat can be represented by Formula I—((Ar₁X₁—Ar₂—X₂Ar₃—X₃)_(m)—Ar₁X₁—Ar₂—)_(a)/((—Ar₄—X₄—Ar₅—X₅—Ar₆—X₆)_(n)—Ar₄—X₄—Ar₅—)_(b)/(Ar₇—X₇—Ar₈)_(c)—R₁—Ar₉—Y—Ar₁₀—R₂—  FormulaIwhere the first group (Ar₁X₁—Ar₂—X₂Ar₃—X₃)_(m)—Ar₁X₁—Ar₂— corresponds to(AB)_(m)A, the second group (Ar₄—X₄—Ar₅—X₅—Ar₆—X₆)_(n)—Ar₄—X₄—Ar₅—corresponds to (CD)_(n)C, where (AB)_(m)A and (CD)_(n)C may be the sameor different. (Ar₇—X₇—Ar₈) is a monomer that is modified to contain anion conducting group and R₁—Ar₉—Y—Ar₁₀—R₂— is a linking monomer. In apreferred embodiment, (AB)_(m)A and (CD)_(n)C are different.

In this formula, Ar₁, Ar₂, Ar₄, Ar₅, Ar₇, Ar₈, Ar₉, Ar₁₀, areindependently phenyl, substituted phenyl napthyl, terphenyl, arylnitrile, substitute aryl nitrile, and one or more of Ar₇ and/or one ormore of Ar₈ further comprise one or more pendant an ion conductinggroups, X₁ and X₄ are independently —C(O)— or —S(O)₂, X₂, X₃, X₅ and X₆are independently —O— or —S—; X₇ is a bond, —C(O)— or S(O)₂—.

Ar₃ and Ar₆ are the same or different from each other and are

wherein the ion conductive group comprises —SO₃H, —COOH, —HPO₃H or—SO₂NH—SO₂—RF where RF is a perfluorinated hydrocarbon having 1-20carbon atoms and said ion conducting group are pendant to the copolymerbackbone;

-   R₁ and R₂ are independently —O— or —S—.-   wherein a, b and c are independently between 0.01 and 0.98 and    a+b+c=1,-   wherein m is between 1 and 12, n is between 1 and 12,-   and wherein Y is a bond, —C(O)—, or —S(O₂)—, and Ar₁₀ may be present    or absent when Y is a bond.

In some embodiments utilizing a single hydrophobic oligomer, when theion conducting monomer used to make the copolymer is SBisK, the linkingmonomer is not BisK.

In some embodiments of this or other formulas herein, at least one of mor n=1. In other embodiments, m and n are each at least 2.

The first oligomer —(Ar₁X₁—Ar₂—X₂Ar₃—X₃)_(m)—Ar₁X₁—Ar₂—; the secondoligomer (Ar₄—X₄—Ar₅—X₅—Ar₆—X₆)_(n)—Ar₄—X₄—Ar₅—, and the ion conductingmonomer Ar₇—X₇—Ar₈ are randomly linked via linking monomerR₁—Ar₉—Y—Ar₁₀—R₂—.

In other embodiments, three or more different hydrophobic oligomers areused.

A particular preferred copolymer of the invention comprises Formula II:

wherein Ar is:

and wherein a is between 0.05 and 0.2, b is between 0.01 and 0.2 and cis between 0.5 and 0.95. In a preferred embodiment, a=0.13, b=0.036 andc=0.83.

In another preferred embodiment the invention comprises a copolymer ofFormula III.

Another preferred embodiment is the coolymer of Formula IV.

The ion conductive polymers can be used to formulate proton exchangemembranes (PEMs) catalyst coated membranes (CCMs), membrane electrodeassemblies (MEAs) and fuel cells comprising the PEM membrane.

The foregoing membranes find particular utility in hydrogen fuel cellsalthough they may be used with other fuels such as direct methanol fuelcells. Such fuel cells can be used in electronic devices, both portableand fixed, power supplies including auxiliary power units (APU's) and aslocomotive power for vehicles such as automobiles, aircraft and marinevessels and APU's associated therewith.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 demonstrates the conductivity versus temperature for a PEM madefrom the copolymer of Example 1 (a block copolymer) and a randomcopolymer made from the same components.

FIG. 2 depicts the fuel cell performance for using the copolymer ofExample 1 under various conditions.

FIG. 3 demonstrates the effect of relative humidity on the cell voltageof fuel cells containing the copolymer of Example 1 as compared toNafion® 112.

FIG. 4 depicts the polarization curves and power density for the MEAsmade in Examples 22, 23 and 24. MEA testing conditions: 6 mg/cm² Pt—Ruin anode, 4 mg/cm² Pt in cathode, 60° C. cell temperature, 2.5stoichiometric air flow, 1M methanol fuel.

FIG. 5 depicts the polarization curves and power density for MEAs 23 and24. MEA testing conditions: 6 mg/cm2 Pt—Ru in anode, 4 mg/cm2 Pt incathode, 60° C. cell temperature, 2.5 stoichiometric air flow, 1Mmethanol fuel.

FIG. 6 depicts polarization curves and power densities for MEAs fromExample. MEA testing conditions: 6 mg/cm2 Pt—Ru in anode, 4 mg/cm2 Pt incathode, 2.5 stoichiometric air flow, 1M methanol fuel.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the invention provides ion conductive copolymerscomprising (1) first oligomers, (2) optionally, second oligomers, (3)ion conductive monomers and (4) linking monomers. The oligomerspreferably are hydrophobic and together with ion conducting monomers arerandomly dispersed between linking monomers. When a single hydrophobicoligomer and ion conducting monomer are randomly dispersed in a polymerbackbone, it is preferred in some embodiments that when SBisK is the ionconducting monomer that BisK is not used in combination with it to formthe copolymer.

In another aspect, one of the first or second oligomer is a hard polymerrelative to the other. Generally, the relative hardness or softness ofone polymer versus another can be determined by comparing the glasstransition temperatures for each of the first and second oligomers. Ahigher glass transition temperature indicates that the oligomer isharder than the one used for comparison. A determination of whether aparticular monomer is harder or softer than another can be madecomparing the glass transition temperature of homomonomers.Alternatively, the first monomer and third monomer in the first andsecond oligomers are the same allowing monomers 2 and 4 to be varied soas to compare the relative hardness of one versus the other.

Uses of such polymeric materials include the formation of polymerelectrolyte membranes (PEMs), catalyst coated membranes (CCM's) andmembrane electrolyte assemblies (MEA's) which may be used in fuel cellsand the like.

In a preferred embodiment, the ion conductive copolymer comprises afirst oligomer comprising first and second comonomers, a second oligomercomprising third and fourth comonomers (at least one of which isdifferent from one of the comonomers of the first oligomer) and at leastone monomer comprising an ion conducting group. Each of the oligomers,the ion conducting monomer and a linking monomer form the ion conductivecopolymer. Some of the ion conductive monomers comprise an ionconducting group that facilitates the transport of ions such as H⁺within and through the ion conducting copolymer.

General methods for the preparation of ion conducting copolymers are asfollows. The methods include the steps of combining a first comonomerwith a second comonomer to form a first oligomer and separatelycombining a third and fourth comonomer to form a second oligomer. Thefirst and third comonomer have at least two leaving groups and thesecond and fourth comonomers have at least two displacing groups. In oneaspect, the first and third comonomers are in a molar excess relative tothe first comonomer, thereby forming first and second oligomers withleaving groups on the end of the first and second oligomer. The ionconductive monomer preferably also has two leaving groups. The linkingmonomer has at least two displacing groups.

The term “leaving group” is intended to include those functionalmoieties that can be displaced by a nucleophilic moiety found,typically, in another monomer. Leaving groups are well recognized in theart and include, for example, halides (chloride, fluoride, iodide,bromide), tosyl, mesyl, etc. In certain embodiments, the monomer has atleast two leaving groups, which are “para” to each other with respect tothe aromatic monomer to which they are attached.

The term “displacing group” is intended to include those functionalmoieties that can act typically as nucleophiles, thereby displacing aleaving group from a suitable monomer. The result is that the monomer towhich the displacing group is attached becomes attached, generallycovalently, to the monomer to which the leaving group was associatedwith. The displacing group becomes R₁ and R₂ as set forth above. Anexample of this is the displacement of fluoride groups from aromaticmonomers by phenoxide, alkoxide or sulfide ions associated with aromaticmonomers.

An example of the synthesis of a first and a second oligomer is asfollows where LG is a leaving group and DG a displacement group.

The first oligomer is made by combining:

when comonomer A is in excess

The second oligomer is similarly made:

when comonomer C is in excess.

First oligomer I, second oligomer II and an ion conducting monomer withtwo leaving groups and a linking monomer with two displacement groupsare combined in a reaction vessel to form the ion conducting copolymer.Alternatively, the leaving groups and displacement groups can beexchanged. In either of these approaches, the copolymers can berepresented by formula I:—((Ar₁X₁—Ar₂—X₂Ar₃—X₃)_(m)—Ar₁—X₁—Ar₂—)_(a)/((Ar₄—X₄—Ar₅—X₅—Ar₆—X₆)_(n)—Ar₄—X₄—Ar₅—)_(b)/(Ar₇—X₇—Ar₈)_(c)—R₁Ar₉—Y—Ar₁₀—R₂—  FormulaIwhere Ar₁, Ar₂, Ar₄, Ar₅, Ar₇, Ar₈, Ar₉ and Ar₁₀ are independentlyphenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitutedaryl nitrile, and Ar₇ and/or Ar₈ further comprises an ion conductinggroup, X₁ and X₄ are independently —C(O)— or —S(O)₂, X₂, X₃, X₅ and X₆are independently —O— or —S—; X₇ is a bond, —C(O)— or —S(O)₂—.

Ar₃ and Ar₆ are the same or different from each other and are

wherein the ion conductive group comprises —SO₃H, —COOH, —HPO₃H or—SO₂NH—SO₂—RF where RF is a perfluorinated hydrocarbon having 1-20carbon atoms and said ion conducting group are pendant to the copolymerbackbone;

-   R₁ and R₂ are independently —O—, or —S—-   wherein a, b and c are independently between 0.01 and 0.98 and    a+b+c=1,-   wherein m is between 1 and 12, n is between 1 and 12,-   and wherein Y is a bond, —C(O)—, or —S(O₂) and Rr₁₀ may be present    or absent when Y is a bond.

In a preferred embodiment Ar₃ and Ar₆ are different from each other.

It is to be understood that the different oligomers and ion conductingmonomer may combine head or tail to the linking monomer thus introducinganother level of randomness in the polymer so formed.

In these and other formulas, m and n are independently 1-12, morepreferably 1-10, and more preferably 2-8, and most preferably 3-6. In aparticularly preferred embodiment, m and n=4. In some embodiments ofthis or other formulas herein at least one of m or n is 2. In others, mand n are at least 2.

In some embodiments, when SBisK is used as the ion conducting monomer,BisK is not used in combination with SBisK.

The mole fraction of the various components as defined by a, b and c areas follows. a is preferably between 0.05-0.4, more preferably between0.05-0.25, and most preferably between 0.05 and 0.15. b is preferablybetween 0.01-0.04, more preferably between 0.05 and 0.3, and mostpreferably between 0.05 and 0.2. c is preferably between 0.2-0.94, andmore preferably between 0.5 and 0.94.

The mole percent of ion conducting groups in the ion conductingcopolymer is calculated as follows: c divided by a(n+1)+b(m+1)+c. Inusing this formula, the mole percent of a monomer containing a singleion conducting group is preferably between 30 and 70%, or morepreferably between 40 and 60%, and most preferably between 45 and 55%.When more than one conducting group is contained within the ionconducting monomer, such percentages are multiplied by the total numberof ion conducting groups per monomer. Thus, in the case of a monomercomprising two sulfonic acid groups, the preferred sulfonation is 60 to140%, more preferably 80 to 120%, and most preferably 90 to 110%.Alternatively, the amount of ion conducting group can be measured by theion exchange capacity (IEC). By way of comparison, Nafion® typically hasa ion exchange capacity of 0.9 meq/gm. In the present invention, it ispreferred that the IEC be between 0.9 and 3.0 meq per gram, morepreferably between 1.0 and 2.5 meq per gram, and most preferably between1.6 and 2.2 meq per gram.

The foregoing ranges can be readily adapted for use in defining otherformulas contained herein.

In an alternative embodiment, comonomer II and comonomer IV are inexcess and produce oligomer IA and IIA as follows:DG-(—(Ar₃—X₃—Ar₁—X₁—Ar₂—X₂—)_(m)Ar₃-DG  Oligomer IADG-(—(Ar₆—X₆—Ar₄—X₄—Ar₅—X₅—)_(n)Ar₆-DG  Oligomer IIA

When oligomers IA and IIA are used in combination with an ion conductingmonomer comprising two displacement groups and a linking monomercomprising two leaving groups, the copolymer so produced can berepresented by formula V:(Ar₃—X₃—Ar₁—X₁Ar₂X₂)_(m)—Ar₃—)_(a)/(—Ar₆—X₆—Ar₄—X₄—Ar₅—X₅)_(n)—Ar₆—)_(b)/(—Ar₇—X₇—Ar₁)_(c)—R₈—Ar₉—Y—Ar₁₀—R₂  FormulaVwherein each of the components are as previously described.

In another embodiment, the oligomers have different hardness as comparedto each other. Formula VI is an example of such a situation:—((Ar₁X₁—Ar₂—X₂Ar₃—X₃)_(m)—Ar₁X₁Ar₂—)_(a)/((Ar₄—X₄—Ar₅—X₅—Ar₆—X₆)_(n)—Ar₄X₄Ar₅—)_(b)/(Ar₇—X₇—Ar₈)_(c)—R₁Ar₉—Y—Ar₁₀—R₂—  FormulaVIwhere Ar₁, Ar₂, Ar₄, Ar₅, Ar₇, Ar₈, Ar₉ and Ar₁₀ are independentlyphenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitutedaryl nitrile, and Ar₇ and/or Ar₈ further comprise an ion conductinggroup, X₁ and X₄ are independently —C(O)— or —S(O)₂, X₂, X₃, X₅ and X₆are independently —O— or —S—; X₇ is a bond, —C(O)— or S(O)₂—.

The Ar₃ monomers are the same or different from each other and are

where the Ar₆ monomers are the same or different from each other and are

wherein the ion conductive group comprises —SO₃H, —COOH, —HPO₃H or—SO₂NH—SO₂—RF where RF is a perfluorinated hydrocarbon having 1-20carbon atoms and said ion conducting group are pendant to the copolymerbackbone;

-   R₁ and R₂ are independently —O— or —S—.-   wherein a, b and c are independently between 0.01 and 0.98 and    a+b+c=1,-   wherein m is between 1 and 10, n is between 1 and 10,-   and wherein Y is a bond, —C(O)—, or —S(O₂)—, and Ar₁₀ may be present    or absent when Y is a bond.

Similarly, Formula V can be modified such that Ar₃ and Ar₆ are selectedfrom the aromatic groups as set forth in Formula VI.

The preparation of the disclosed first and second oligomer and choice ofion conducting and linking monomer provide flexibility in theformulation of the ion conductive copolymer. Selected first and secondoligomers and monomers (both ion conductive and linking) can be combinedin defined ratios to provide copolymers having a variety of physical andchemical properties.

A particularly preferred embodiment is:

wherein Ar is

wherein a is between 0.05 and 0.2, b is between 0.01 and 0.2 and c isbetween 0.5 and 0.95. In a preferred embodiment, a=0.13, b=0.036 andc=0.83.

Another preferred embodiment is the coolymer of formula IIC.

In alternate embodiments, one oligomer is used rather than two or moredifferent oligomers. Where this is the case. in some embodiments, it ispreferred when SBisK is the only ion conducting monomer that the BisKmonomer is not used. In another embodiment, where a single oligomer isused, the copolymer is other than that set forth in Examples 63-116herein.

Polymer membranes may be fabricated by solution casting of the ionconductive copolymer. Alternatively, the polymer membrane may befabricated by solution casting the ion conducting polymer the blend ofthe acid and basic polymer.

When cast into a membrane for use in a fuel cell, it is preferred thatthe membrane thickness be between 0.1 to 10 mils, more preferablybetween 1 and 6 mils, most preferably between 1.5 and 2.5 mils, and itcan be coated over polymer substrate

As used herein, a membrane is permeable to protons if the proton flux isgreater than approximately 0.005 S/cm, more preferably greater than 0.01S/cm, most preferably greater than 0.02 S/cm.

As used herein, a membrane is substantially impermeable to methanol ifthe methanol transport across a membrane having a given thickness isless than the transfer of methanol across a Nafion® membrane of the samethickness. In preferred embodiments the permeability of methanol ispreferably 50% less than that of a Nafion® membrane, more preferably 75%less and most preferably greater than 80% less as compared to theNafion® membrane.

After the ion conducting copolymer has been formed into a membrane, itmay be used to produce a catalyst coated membrane (CCM). As used herein,a CCM comprises a PEM when at least one side and preferably both of theopposing sides of the PEM are partially or completely coated withcatalyst. The catalyst is preferable a layer made of catalyst andionomer. Preferred catalysts are Pt and Pt—Ru. Preferred ionomersinclude Nafion® and other ion conductive polymers. In general, anode andcathode catalysts are applied onto the membrane by well establishedstandard techniques. For direct methanol fuel cells, platinum/rutheniumcatalyst is typically used on the anode side while platinum catalyst isapplied on the cathode side. For hydrogen/air or hydrogen/oxygen fuelcells platinum or platinum/ruthenium is generally applied on the anodeside, and platinum is applied on the cathode side. Catalysts may beoptionally supported on carbon. The catalyst is initially dispersed in asmall amount of water (about 100 mg of catalyst in 1 g of water). Tothis dispersion a 5% ionomer solution in water/alcohol is added(0.25-0.75 g). The resulting dispersion may be directly painted onto thepolymer membrane. Alternatively, isopropanol (1-3 g) is added and thedispersion is directly sprayed onto the membrane. The catalyst may alsobe applied onto the membrane by decal transfer, as described in the openliterature (Electrochimica Acta, 40: 297 (1995)).

The CCM is used to make MEA's. As used herein, an MEA refers to an ionconducting polymer membrane made from a CCM according to the inventionin combination with anode and cathode electrodes positioned to be inelectrical contact with the catalyst layer of the CCM.

The electrodes are in electrical contact with the catalyst layer, eitherdirectly or indirectly, when they are capable of completing anelectrical circuit which includes the CCM and a load to which the fuelcell current is supplied. More particularly, a first catalyst iselectrocatalytically associated with the anode side of the PEM so as tofacilitate the oxidation of hydrogen or organic fuel. Such oxidationgenerally results in the formation of protons, electrons and, in thecase of organic fuels, carbon dioxide and water. Since the membrane issubstantially impermeable to molecular hydrogen and organic fuels suchas methanol, as well as carbon dioxide, such components remain on theanodic side of the membrane. Electrons formed from the electrocatalyticreaction are transmitted from the cathode to the load and then to theanode. Balancing this direct electron current is the transfer of anequivalent number of protons across the membrane to the anodiccompartment. There an electrocatalytic reduction of oxygen in thepresence of the transmitted protons occurs to form water.

In one embodiment, air is the source of oxygen. In another embodiment,oxygen-enriched air is used.

The membrane electrode assembly is generally used to divide a fuel cellinto anodic and cathodic compartments. In such fuel cell systems, a fuelsuch as hydrogen gas or an organic fuel such as methanol is added to theanodic compartment while an oxidant such as oxygen or ambient air isallowed to enter the cathodic compartment. Depending upon the particularuse of a fuel cell, a number of cells can be combined to achieveappropriate voltage and power output. Such applications includeelectrical power sources for residential, industrial, commercial powersystems and for use in locomotive power such as in automobiles. Otheruses to which the invention finds particular use includes the use offuel cells in portable electronic devices such as cell phones and othertelecommunication devices, video and audio consumer electronicsequipment, computer laptops, computer notebooks, personal digitalassistants and other computing devices, GPS devices and the like. Inaddition, the fuel cells may be stacked to increase voltage and currentcapacity for use in high power applications such as industrial andresidential sewer services or used to provide locomotion to vehicles.Such fuel cell structures include those disclosed in U.S. Pat. Nos.6,416,895, 6,413,664, 6,106,964, 5,840,438, 5,773,160, 5,750,281,5,547,776, 5,527,363, 5,521,018, 5,514,487, 5,482,680, 5,432,021,5,382,478, 5,300,370, 5,252,410 and 5,230,966.

Such CCM and MEM's are generally useful in fuel cells such as thosedisclosed in U.S. Pat. Nos. 5,945,231, 5,773,162, 5,992,008, 5,723,229,6,057,051, 5,976,725, 5,789,093, 4,612,261, 4,407,905, 4,629,664,4,562,123, 4,789,917, 4,446,210, 4,390,603, 6,110,613, 6,020,083,5,480,735, 4,851,377, 4,420,544, 5,759,712, 5,807,412, 5,670,266,5,916,699, 5,693,434, 5,688,613, 5,688,614, each of which is expresslyincorporated herein by reference.

The CCM's and MEA's of the invention may also be used in hydrogen fuelcells which are known in the art. Examples include U.S. Pat. Nos.6,630,259; 6,617,066; 6,602,920; 6,602,627; 6,568,633; 6,544,679;6,536,551; 6,506,510; 6,497,974, 6,321,145; 6,195,999; 5,984,235;5,759,712; 5,509,942; and 5,458,989 each of which are expresslyincorporated herein by reference.

The ion conducting polymer membranes of the invention also find use asseparators in batteries. Particularly preferred batteries are lithiumion batteries.

EXAMPLES

A list of some of the monomers used in practicing the invention are setforth in Table I.

TABLE I Monomers Used Acronym Full name Molecular weight Chemicalstructure 1) Difluoro-end monomers Bis K 4,4′-Difluorobenzophenone218.20

Bis SO₂ 4,4′-Difluorodiphenylsulfone 254.25

S-Bis K 3,3′-disulfonated-4,4′-di-fluorobenzophone 422.28

2) Dihydroxy-end monomers Bis AF (AFor 6F)2,2-Bis(4-hydroxyphenyl)hexa-fluoropropaneor4,4′-(hexafluoroisopropylidene)di-phenol 336.24

BP Biphenol 186.21

Bis FL 9,9-Bis(4-hydroxyphenyl)fluorene 350.41

Bis Z 4,4′-cyclohexylidenebisphenol 268.36

Bis S 4,4′-thiodiphenol 218.27

3) Dithiol-end monomers 35 4,4′-thiolbisbenzenethiol

This Table also provides acronyms used for the various starting monomersas well as the monomers as contained within ion conductive copolymers.Other acronyms include the following:

Acronym:

-   -   R=random copolymer, Bi=block copolymer    -   RK=random copolymer based on Bis K and S-BisK,    -   RS=random copolymer based on Bis SO₂ and S-BisK    -   B=biphenol, AF=BisAF (6F), FL=BisFL, Z=BisZ    -   BIK=Block copolymer containing BisK in its formulation    -   Bl_=Block copolymer without BisK in its formulation

Abbreviations include:

-   -   IEC: Ion Exchange Capacity (meq/g), IV: Inherent viscosity        (dl/g)    -   CD: conductivity (S/cm)

Example 1 BL_FL4AF4-B/50, Oligomers Used: FL4+AF4

Oligomer 1 (FL4, F-end): m or n=4

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, a thermometer probe connected with a nitrogen inlet, and aDean-Stark trap/condenser, 4,4′-difluorobenzophone (BisK, 34.91 g, 0.16mol), 9,9-bis(4-hydroxyphenyl)fluorene (Bis FL, 42.05 g, 0.12 mol), andanhydrous potassium carbonate (19.9 g, 0.192 mol) were dissolved in amixture of 220 ml of DMSO and 110 ml of Toluene. The reaction mixturewas slowly stirred under a slow nitrogen stream. After heating at ˜120°C. for 1 h and was raised to ˜140° C. for 2 h, and finally to ˜160° C.for 3 h. After cooling to ˜70° C. with continuing stirring, the solutionwas dropped into 1 L of cooled methanol with a vigorous stirring. Theprecipitates were filtrated and washed with DI-water four times anddried at 80° C. overnight, and then dried at 80° C. under vacuum for 2days. The oligomer has the following structure:

Oligomer 2 (AF4, F-end): m or n=4

This oligomer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 34.91 g),4,4′-(hexafluoroisopropylidene)diphenol (Bis AF, 40.35 g), and anhydrouspotassium carbonate (19.9 g) in a mixture of 220 ml of DMSO and 110 mlof Toluene. The oligomer has the following structure:

Polymerization

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,3,3′-disulfonated-4,4′-difluorobenzophone (S-BisK, 17.61 g), Oligomer 1(15.16 g), Oligomer 2 (4.10 g), biphenol (9.31 g), and anhydrouspotassium carbonate (8.29 g) were dissolved in a mixture of DMSO andToluene (about 20% solid concentration). The mixture was heated totoluene flux with stirring, keeping the temperature at 140° C. for 6 h,then increase temperature to 173-175° C. for 4 h. The reaction mixturewas precipitated from methanol to get the crude product and washed withDI-water. The polymer was treated in 0.5 mol H₂SO₄ aqueous solution at80° C. for 1 hour to produce the proton form of sulfonic acid group inthe polymer and washed with deionized water and dried at 80° C.overnight, and then dried at 80° C. under vacuum for 2 days.

Dried polymer was dissolved in dimethylacetamide (DMAc) to make asolution (25 wt %) and cast, and dried at 80° C. to make a membrane (2.0mil thick). The obtained membrane was treated in 1.5 mol H₂SO₄ aqueoussolution to get rid of DMAc residue and rinsed in DI-water until noH₂SO₄ residue was detected, and dried at 80° C.

The polymer membrane was swollen in water at room temperature and thepolymer membrane conductivity was measured by AC impedance. The driedmembrane was swollen in a boiling water for 1 hour to measurewater-uptake and swelling by area.

This polymer has an inherent viscosity of 1.52 dl/g in DMAc (0.25 g/dl).IEC is 1.97 meq/g. Conductivity: 0.093 S/cm (0.112 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 50%, water-uptake afterboiling the membrane in water 1 hr 64%

Example 2 BL_FL4 AF4-B45 Oligomers Used: FL4+AF4

This block polymer was synthesized and treated in a similar way asdescribed in example 1: S-BisK (16.98 g), Oligomer 1 (15.86 g), Oligomer2 (6.83 g), biphenol (9.31 g), and anhydrous potassium carbonate (8.29g) were dissolved in a mixture of DMSO and Toluene (about 20% solidconcentration).

This polymer has an inherent viscosity of 1.11 dl/g in DMAc (0.25 g/dl).IEC is 1.78 meq/g. Conductivity: 0.081 S/cm (0.099 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 40%, water-uptake afterboiling the membrane in water 1 hr: 57%

Example 3 BL_FL4 AF4-B/41 Oligomers Used: FL4+AF4

This block polymer was synthesized in a similar way as described inexample 1: S-BisK (16.47 g), Oligomer 1 (14.0 g), Oligomer 2 (11.38 g),biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) weredissolved in a mixture of DMSO and Toluene (about 20% solidconcentration).

This polymer has an inherent viscosity of 1.30 dl/g in DMAc (0.25 g/dl).IEC is 1.64 meq/g. Conductivity: 0.068 S/cm (0.092 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 35%, water-uptake afterboiling the membrane in water 1 hr: 52%

Example 4 BL_FL4 AF8-B/48 Oligomers Used: FL4+AF8

Oligomer 3 (AF8, F-end): m or n=8

This oligomer was synthesized in a similar way as described in theoligomer 1 synthesis: BisK (34.91 g), Bis AF (47.07 g), and anhydrouspotassium carbonate (23.22 g) in a mixture of 220 ml of DMSO and 110 mlof Toluene. This structure is the same as oligomer 2 except that the AFunit is repeating 8 times rather than 4 times.

Polymerization

The block polymer was synthesized in a similar way as described inexample 1: S-BisK (17.82 g), Oligomer 1 (14.0 g), Oligomer 3 (7.8 g),biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) weredissolved in a mixture of DMSO and Toluene (about 20% solidconcentration).

This polymer has an inherent viscosity of 1.79 dl/g in DMAc (0.25 g/dl).IEC is 1.87 meq/g. Conductivity: 0.092 S/cm (0.100 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 45%, water-uptake afterboiling the membrane in water 1 hr: 63%

Example 5 BL_FL4 AF4-B/42 Oligomers Used: FL4+AF8

This block polymer was synthesized in a similar way as described inexample 1: S-BisK (17.31 g), Oligomer 1 (14.0 g), Oligomer 3 (13.0 g),biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) weredissolved in a mixture of DMSO and Toluene (about 20% solidconcentration).

This polymer has an inherent viscosity of 1.73 dl/g in DMAc (0.25 g/dl).IEC is 1.65 meq/g. Conductivity: 0.074 S/cm (0.100 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 38%, water-uptake afterboiling the membrane in water 1 hr: 58%

Table II sets forth the properties of the copolymer made in Examples 1-5as well as other oligomeric block copolymers.

TABLE II Properties of Oligomeric Block Membranes CD Swell- Water-(S/cm) CD ing uptake Polymer IEC IV at rt (boiled) % % BlK_AF4-AF/351.23 1.12 0.025 0.060 35.7 42.0 BlK_AF10-AF/35 1.23 1.14 0.049 0.045 127160 BlK_FL4-AF/41 1.40 1.19 0.036 0.080 43.8 58.8 BlK_FL4- 1.58 1.450.048 0.088 43.2 58.3 B50AF50/42 Bl_FL4AF4-B/41 1.64 1.30 0.068 0.09234.7 52.1 Bl_FL4-B/41 1.63 1.54 0.061 0.087 35.0 48.5 Bl_FL4AF8-B/421.65 1.73 0.074 0.100 37.5 58.3 Bl_FL4S8-B/42 1.71 1.36 0.072 0.097 41.163.7 Bl_FL4AF4-B/45 1.78 1.11 0.081 0.099 39.8 57.2 BlK_FL4-AF/41 1.411.11 0.033 0.075 51.3 62.5 Bl_FL4AF4-B/50 1.97 1.52 0.093 0.112 50.263.9 Bl_FL4AF8-B/48 1.87 1.79 0.092 0.100 62.8 45.2 Bl_AF8-B/45 1.781.21 0.119 0.103 80.9 36.3

Example 6 BL_FL4 S8-B/42 Oligomers Used: FL4+S8)

Oligomer 4 (S8, F-end): m or n=8

This oligomer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorodiphenylsulfone (Bis SO₂, 40.68 g), 4,4′-thiodiphenol (BisS, 30.56 g), and anhydrous potassium carbonate (23.22 g) in a mixture of220 ml of DMSO and 110 ml of Toluene. S8 has the following structure:

Polymerization

This block polymer was synthesized in a similar way as described inexample 1: S-BisK (17.31 g), Oligomer 1 (14.0 g), Oligomer 4 (11.14 g),biphenol (9.31 g), and anhydrous potassium carbonate (8.29 g) weredissolved in a mixture of DMSO and Toluene (about 20% solidconcentration).

This polymer has an inherent viscosity of 1.36 dl/g in DMAc (0.25 g/dl).IEC is 1.71 meq/g. Conductivity: 0.072 S/cm (0.097 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 41%, water-uptake afterboiling the membrane in water 1 hr: 64%

Example 7 BL_FL4-B/41Ooligomer Used: FL4 only

This block polymer was synthesized in a similar way as described inexample 1: S-BisK (16.47 g), Oligomer 1 (25.66 g), biphenol (9.31 g),and anhydrous potassium carbonate (8.29 g) were dissolved in a mixtureof DMSO and Toluene (about 20% solid concentration).

This polymer has an inherent viscosity of 1.54 dl/g in DMAc (0.25 g/dl).IEC is 1.63 meq/g. Conductivity: 0.061 S/cm (0.087 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 35%, water-uptake afterboiling the membrane in water 1 hr: 49%

Example 8 BLK_FL4-B50 AF50/42 Oligomer Used: FL4 Only

This block polymer was synthesized in a similar way as described inexample 1: Bis K (2.75 g), S-BisK (13.26 g), Oligomer 1 (14.0 g),biphenol (4.66 g), Bis AF (8.41 g), and anhydrous potassium carbonate(8.29 g) were dissolved in a mixture of DMSO and Toluene (about 20%solid concentration).

This polymer has an inherent viscosity of 1.45 dl/g in DMAc (0.25 g/dl).IEC is 1.58 meq/g. Conductivity: 0.048 S/cm (0.088 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 43%, water-uptake afterboiling the membrane in water 1 hr: 58%

Example 9 BLK_FL4-AF/41 Oligomer Used: FL4 Only

This block polymer was synthesized in a similar way as described inexample 1: Bis K (2.4 g), S-BisK (13.51 g), Oligomer 1 (16.33 g), Bis AF(16.81 g), and anhydrous potassium carbonate (8.29 g) were dissolved ina mixture of DMSO and Toluene (about 20% solid concentration). Thispolymer has an inherent viscosity of 1.19 dl/g in DMAc (0.25 g/dl). IECis 1.40 meq/g. Conductivity: 0.036 S/cm (0.080 S/cm, boiled in water 1hr), swelling by area in boiled water 1 hr: 44%, water-uptake afterboiling the membrane in water 1 hr: 59%

Example 10 B:_AF8-B/45 Oligomer Used: AF8 (oligomer 3) Only

This block polymer was synthesized in a similar way as described inexample 1: S-BisK (18.62 g), Oligomer 3 (25.57 g), biphenol (9.31 g),and anhydrous potassium carbonate (8.29 g) were dissolved in a mixtureof DMSO and Toluene (about 20% solid concentration).

This polymer has an inherent viscosity of 1.21 dl/g in DMAc (0.25 g/dl).IEC is 1.78 meq/g. Conductivity: 0.119 S/cm (0.103 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 36%, water-uptake afterboiling the membrane in water 1 hr: 81%

Example 11 BLK_AF10-AF/35 Oligomers Used: AF10 Only

Oligomer 5 (AF10, F-end): DP=10

This oligomer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions: BisK (34.91 g), BisAF (48.42 g), and anhydrous potassium carbonate (23.88 g) in a mixtureof 220 ml of DMSO and 110 ml of Toluene.

Polymerization

This block polymer was synthesized in a similar way as described inexample 1: BisK (2.34 g), S-BisK (14.57 g), Oligomer 5 (25.74 g), BisAF(16.81 g), and anhydrous potassium carbonate (8.29 g) were dissolved ina mixture of DMSO and Toluene (about 20% solid concentration).

This polymer has an inherent viscosity of 1.14 dl/g in DMAc (0.25 g/dl).IEC is 1.23 meq/g. Conductivity: 0.049 S/cm (0.045 S/cm, boiled in water1 hr), swelling by area in boiled water 1 hr: 127%, water-uptake afterboiling the membrane in water 1 hr: 160%

The membrane conductivity: 0.060 S/cm, Swelling after boiled: 68% byarea, water up-take:84%

Example 12 Synthesis of Partial Block Polymer with Non-sulfonatedHydrophobic Segment

Fluorine end group oligomer (difluorophenylsulfone/4,4′-thiolbisbenezenesulfide) preparation (segment size n=4)

In a 250 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-Thiolbisbenezenethiol (15.0246 g), difluorophenyl sulfone (20.34g), anhydrous potassium carbonate (11 g) were dissolved in a mixtureDMSO and Toluene (about 20% solid concentration). The mixture was heatedto toluene flux with stirring, keeping the temperature at 140° C. for 4h, then increase temperature to 175° C. for 4 h. The reaction mixtureprecipitates from methanol to get the rude product, and then washed byhot water four times. Dry at 80 C oven for one day and 75 C vacuum ovenfor 2 days.

Polymerization

In a 250 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-Thiolbisbenezenethiol (12.5205 g), difluorophenyl sulfone (6.102g), sulfonated difluorophenyl sulfone (901664 g), oligomer (12.672 g,n=4, fluorine end of difluorophenyl sulfone/4,4′-thiolbisbenezenesulfidecomposition), anhydrous potassium carbonate (9.0 g) were dissolved in amixture DMSO and Toluene (about 20% solid concentration). The mixturewas heated to toluene flux with stirring, keeping the temperature at140° C. for 6 h, then increase temperature to 173-175° C. for 4-4.5 h.The reaction mixture precipitates from methanol to get the rude product.

The membrane conductivity: 0.076 S/cm, Swelling after boiled: 50% byarea, water up-take:41%

Example 13 F-ended Oligomer 1: DP=4

In a 500 mL three necked round flask, equipped with a mechanicalstirrer, a thermometer probe connected with a nitrogen inlet, and aDean-Stark trap/condenser, 4,4′-difluorobenzophone (BisK, 34.91 g, 0.16mol), 9,9-bis(4-hydroxyphenyl)fluorene (42.05 g, 0.12 mol), andanhydrous potassium carbonate (25.87 g, 0.187 mol), 220 mL of DMSO and110 mL of Toluene. The reaction mixture was slowly stirred under a slownitrogen stream. After heating at ˜85° C. for 1 h and at ˜120° C. for 1h, the reaction temperature was raised to ˜140° C. for 3 h, and finallyto ˜170° C. for 2 h. After cooling to ˜70° C. with continuing stirring,the solution was dropped into 1 L of methanol with a vigorous stirring.The precipitates were filtrated and washed with de-ionized water fourtimes and dried at 80° C. overnight, and then dried at 80° C. undervacuum for 2 days.

A block copolymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 6.49 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 13.39 g), Oligomer 7(18.29 g), 1,1-Bis(4-hydroxyphenyl)cyclohexane (BisZ, 26.28 g), andanhydrous potassium carbonate (12.51 g), 216 mL of DMSO and 108 mL ofToluene. The dried polymer was converted into acid form by stirring inhot H₂SO₄ (0.5 M) solution for one hour, followed by de-ionized waterwashing, and dried.

Example 14

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (6.84 g), SBisK(16.76 g), Oligomer 7 (20.90 g), BisZ (21.47 g), and anhydrous potassiumcarbonate (14.37 g).

Example 15

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (5.72 g), SBisK(17.04 g), Oligomer 7 (19.59 g), BisZ (20.12 g), and anhydrous potassiumcarbonate (13.48 g).

Example 16

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (5.27 g), SBisK(19.80 g), Oligomer 7 (20.90 g), BisZ (21.47 g), and anhydrous potassiumcarbonate (14.37 g).

Example 17

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (3.92 g), SBisK(13.48 g), Oligomer 7 (23.51 g), BisZ (16.10 g), and anhydrous potassiumcarbonate (10.78 g).

Example 18

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.16 g), SBisK(15.48 g), Oligomer 7 (31.35 g), BisZ (16.10 g), and anhydrous potassiumcarbonate (10.78 g).

TABLE 1 Ex-situ Data Summary for Block Polymer Methanol crossover σr.t./boiled Water λ IEC [η]₂₅ SW r.t./boiled (mg · mil/ uptake (H₂O/Membrane (meq/g) (dL/g) (%) (S/cm) cc · min · cm²) (%, w/w) H⁺) Example1.20 0.58 32 NA/0.034 NA/0.018 33 15 13 Example 1.30 1.64 35 0.020/0.037NA/0.016 26 11 14 Example 1.40 0.72 56 0.024/0.053 0.010/0.017 40 16 15Example 1.50 0.99 59 0.041/0.058 NA/0.044 43 16 16 Example 1.20 1.00 270.021/0.035 0.003/0.010 25 12 17 Example 1.20 1.44 25 0.023/0.035NA/0.011 25 12 18

Example 19

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (8.52 g), SBisK(13.51 g), Oligomer 7 (20.90 g), 2,2′-Biphenol (14.89 g), and anhydrouspotassium carbonate (14.37 g).

Example 20

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (6.97 g), SBisK(12.00 g), Oligomer 7 (17.76 g), 2,2′-Biphenol (12.66 g), and anhydrouspotassium carbonate (12.22 g).

Example 21

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (7.84 g), SBisK(14.83 g), Oligomer 7 (20.90 g), 2,2′-Biphenol (14.89 g), and anhydrouspotassium carbonate (14.37 g).

Example 22

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (5.41 g), SBisK(14.13 g), Oligomer 7 (27.43 g), 2,2′-Biphenol (13.03 g), and anhydrouspotassium carbonate (12.58 g). MEA 10 contains this block copolymer.

Example 23

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (4.35 g), SBisK(12.67 g), Oligomer 7 (23.51 g), 2,2′-Biphenol (11.17 g), and anhydrouspotassium carbonate (10.78 g). MEA 11 contains this block copolymer.

Example 24

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (4.73 g), SBisK(15.43 g), Oligomer 7 (27.43 g), 2,2′-Biphenol (13.03 g), and anhydrouspotassium carbonate (12.58 g). MEA 12 contains this block copolymer.

Example 25

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.94 g), SBisK(12.33 g), Oligomer 7 (28.73 g), 2,2′-Biphenol (10.24 g), and anhydrouspotassium carbonate (9.88 g).

Example 26

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.86 g), SBisK(14.11 g), Oligomer 7 (31.35 g), 2,2′-Biphenol (11.17 g), and anhydrouspotassium carbonate (10.78 g).

Example 27

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.54 g), SBisK(14.74 g), Oligomer 7 (31.35 g), 2,2′-Biphenol (11.17 g), and anhydrouspotassium carbonate (10.78 g).

Example 28

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (1.80 g), SBisK(12.90 g), Oligomer 7 (26.12 g), 2,2′-Biphenol (9.31 g), and anhydrouspotassium carbonate (8.98 g).

Example 29

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (1.55 g), SBisK(13.39 g), Oligomer 7 (26.12 g), 2,2′-Biphenol (9.31 g), and anhydrouspotassium carbonate (8.98 g).

Example 30

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (1.25 g), SBisK(13.96 g), Oligomer 7 (26.12 g), 2,2′-Biphenol (9.31 g), and anhydrouspotassium carbonate (8.98 g).

TABLE 2 Ex-Situ Data Summary for Block Polymers Methanol crossover σr.t./boiled Water λ IEC [η]₂₅ SW r.t./boiled (mg · mil/ uptake (H₂O/Membrane (meq/g) (dL/g) (%) (S/cm) cc · min · cm²) (%, w/w) H⁺) Example19 1.20 1.74 16 0.027/0.039 0.023/0.024 22 10 Example 20 1.25 2.09 180.030/0.039 0.012/0.015 24 11 Example 21 1.30 2.14 24 0.033/0.0460.014/0.027 27 12 Example 22 1.20 1.48 23 0.026/0.037 0.013/NA 20 9Example 23 1.25 1.59 24 0.030/0.042 0.014/0.024 25 11 Example 24 1.302.08 21 0.034/0.044 0.013/0.023 27 12 Example 25 1.15 1.11 240.026/0.037 NA 24 12 Example 26 1.20 1.67 22 0.031/0.040 NA/0.009 21 10Example 27 1.25 1.45 25 0.034/0.043 NA/0.013 24 11 Example 28 1.30 1.4624 0.038/0.049 0.011/0.027 27 12 Example 29 1.35 1.80 26 0.042/0.0580.016/0.036 27 11 Example 30 1.40 1.30 28 0.041/0.057 0.017/0.035 29 12

TABLE 3 In-Situ Data Summary for Block Polymers Power density MethanolThickness at 0.4 V crossover HFR Membrane (μ) (mW/cm²) (mA/cm²) (Ohm ·cm²) Example 19 44 106 46 0.20 Example 20 56 111 39 0.22 Example 21 56112 44 0.17 Example 22 45 103 40 0.18 Example 23 57 120 45 0.18 Example24 48 120 58 0.14 Example 25 48 110 43 0.18 Example 26 46 122 53 0.14Example 27 52 116 65 0.14 Example 28 58 112 52 0.12 Example 29 57 124 710.12

Example 31

This block polymer was synthesized in a similar way as described inexample 1 synthesis, using following compositions: BisK (4.99 g), SBisK(12.84 g), Oligomer 1 (15.67 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), and anhydrouspotassium carbonate (10.78 g).

Example 32

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (4.70 g), SBisK(13.40 g), Oligomer 7 (15.67 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), and anhydrouspotassium carbonate (10.78 g).

Example 33

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (4.38 g), SBisK(14.01 g), Oligomer 7 (15.67 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), and anhydrouspotassium carbonate (10.78 g).

Example 34

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (3.24 g), SBisK(14.80 g), Oligomer 7 (23.51 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), and anhydrouspotassium carbonate (10.78 g). MEA 22 contains this block copolymer.

Example 35

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.89 g), SBisK(15.48 g), Oligomer 7 (23.51 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), and anhydrouspotassium carbonate (10.78 g). MEA 23 contains this block copolymer.

Example 36

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.49 g), SBisK(16.27 g), Oligomer 7 (23.51 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), and anhydrouspotassium carbonate (10.78 g). MEA 24 contains this block copolymer.

Example 37

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (1.23 g), SBisK(14.00 g), Oligomer 7 (26.12 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (17.32 g), and anhydrouspotassium carbonate (8.98 g).

TABLE 4 Ex-situ Data Summary for Block Polymers 31-37 Methanol crossoverσ r.t./boiled Water λ IEC [η]₂₅ SW r.t./boiled (mg · mil/ uptake (H₂O/Membrane (meq/g) (dL/g) (%) (S/cm) cc · min · cm²) (%, w/w) H⁺) Example31 1.20 1.88 27 0.023/0.040 NA/0.010 25 12 Example 32 1.25 1.65 310.025/0.042 0.010/0.016 26 12 Example 33 1.30 1.86 30 0.030/0.0410.010/0.020 30 13 Example 34 1.20 1.17 28 0.024/0.041 0.010/0.014 25 12Example 35 1.25 1.67 30 0.025/0.045 0.011/0.017 27 12 Example 36 1.301.72 33 0.031/0.048 0.014/0.025 30 13 Example 37 1.20 1.38 270.025/0.038 NA 24 11

TABLE 5 In-Situ Data Summary for Block Polymers 31-37 Power densityMethanol Thickness at 0.4 V crossover HFR Membrane (μ) (mW/cm²) (mA/cm²)(Ohm · cm²) Example 31 54 105 33 0.21 Example 32 52 120 37 0.19 Example33 55 108 40 0.19 Example 34 53 102 33 0.22 Example 35 54 114 33 0.20Example 36 50 122 49 0.16 Example 37 52 100 37 0.18

Example 38

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (6.10 g), SBisK (13.35 g), Oligomer 7 (22.21g), 2,2′-Biphenol (15.83 g), and anhydrous potassium carbonate (15.27g).

Example 39

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (5.88 g), SBisK (14.03 g), Oligomer 7 (22.21g), 2,2′-Biphenol (15.83 g), and anhydrous potassium carbonate (15.27g). MEA 27 contains this block copolymer.

Example 40

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (5.31 g), SBisK (13.88 g), Oligomer 7 (20.90g), 2,2′-Biphenol (14.90 g), and anhydrous potassium carbonate (14.37g).

Example 41

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (3.88 g), SBisK (14.57 g), Oligomer 7 (29.39g), 2,2′-Biphenol (13.96 g), and anhydrous potassium carbonate (13.48g).

Example 42

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (3.66 g), SBisK (15.23 g), Oligomer 7 (29.39g), 2,2′-Biphenol (13.96 g), and anhydrous potassium carbonate (13.47g).

Example 43

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (3.18 g), SBisK (14.93 g), Oligomer 7 (27.43g), 2,2′-Biphenol (13.03 g), and anhydrous potassium carbonate (12.58g).

Example 44

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (1.92 g), SBisK (13.83 g), Oligomer 7 (31.35g), 2,2′-Biphenol (11.17 g), and anhydrous potassium carbonate (10.78g).

Example 45

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (1.71 g), SBisK (14.47 g), Oligomer 7 (31.35g), 2,2′-Biphenol (11.17 g), and anhydrous potassium carbonate (10.78g).

Example 46

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (1.47 g), SBisK (15.20 g), Oligomer 7 (31.35g), 2,2′-Biphenol (11.17 g), and anhydrous potassium carbonate (10.78g).

Example 47

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (3.62 g), SBisK (13.39 g), Oligomer 7 (16.98g), Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (22.52 g), andanhydrous potassium carbonate (11.68 g).

Example 48

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions:2,6-difluorobenzonitrile (2.17 g), SBisK (14.49 g), Oligomer 7 (23.51g), Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), andanhydrous potassium carbonate (10.78 g).

TABLE 6 Ex-situ Data Summary for Block Polymers 26-48 Methanol crossoverσ r.t./boiled Water λ IEC [η]₂₅ SW r.t./boiled (mg · mil/ uptake (H₂O/Membrane (meq/g) (dL/g) (%) (S/cm) cc · min · cm²) (%, w/w) H⁺) Example38 1.20 2.77 17 0.026/0.033 NA/0.007 18 8 Example 39 1.25 1.92 240.031/0.033 NA/0.010 24 11 Example 40 1.30 1.91 26 0.037/0.046 NA 31 11Example 41 1.20 2.23 30 0.029/0.036 NA/0.013 25 12 Example 42 1.25 2.1321 0.034/0.046 NA/0.012 26 11 Example 43 1.30 1.29 27 0.037/0.052 NA 2812 Example 44 1.20 1.36 22 0.030/0.038 NA 22 10 Example 45 1.25 0.93 250.031/0.044 NA 31 14 Example 46 1.30 0.81 25 0.037/0.047 NA 28 12Example 47 1.20 1.13 31 0.023/0.035 NA/0.013 25 12 Example 48 1.20 0.9333 0.024/0.036 NA/0.014 23 11

TABLE 7 In-Situ Data Summary for Block Polymers 38-44, 47 and 48 Powerdensity Methanol Thickness at 0.4 V crossover HFR Membrane (μ) (mW/cm²)(mA/cm²) (Ohm · cm²) Example 38 50 92 31 0.23 Example 39 47 118 36 0.20Example 40 44 130 64 0.13 Example 41 56 110 39 0.22 Example 42 43 106 610.15 Example 43 49 112 57 0.14 Example 44 47 112 42 0.16 Example 47 52106 39 0.22 Example 48 55 118 34 0.21

Example 49

F-ended Oligomer 8: DP=6

This oligomer was synthesized in a similar way as described in theoligomer 13 synthesis, using following compositions: BisK (65.46 g),9,9-bis(4-hydroxyphenyl)fluorene (87.60 g), and anhydrous potassiumcarbonate (26.95 g), 540 mL of DMSO and 270 mL of Toluene.

Example 50

A block polymer was synthesized in a similar way as described in Example13 synthesis, using following compositions: BisK (3.97 g), SBisK (14.82g), Oligomer 8 (22.78 g), Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene(20.78 g), and anhydrous potassium carbonate (10.78 g).

Example 51

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (3.02 g), SBisK(12.90 g), Oligomer 8 (18.98 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (17.32 g), and anhydrouspotassium carbonate (8.98 g).

Example 52

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.70 g), SBisK(13.51 g), Oligomer 8 (18.98 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (17.32 g), and anhydrouspotassium carbonate (8.98 g).

Example 53

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (1.28 g), SBisK(13.34 g), Oligomer 8 (25.63 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (15.59 g), and anhydrouspotassium carbonate (8.08 g).

Example 54

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (0.95 g), SBisK(13.97 g), Oligomer 8 (25.63 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (15.59 g), and anhydrouspotassium carbonate (8.08 g).

Example 55

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (0.61 g), SBisK(14.63 g), Oligomer 8 (25.63 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (15.59 g), and anhydrouspotassium carbonate (8.08 g).

Example 56

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (5.34 g), SBisK(12.16 g), Oligomer 8 (22.78 g), 2,2′-Biphenol (11.17 g), and anhydrouspotassium carbonate (10.78 g).

Example 57

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (4.65 g), SBisK(13.50 g), Oligomer 8 (22.78 g), BisZ (16.10 g), and anhydrous potassiumcarbonate (10.78 g).

Example 58

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (3.97 g), SBisK(14.82 g), Oligomer 8 (22.78 g),Bis(4-hydroxylphenyl)-1,4-diisopropylbenzene (20.78 g), and anhydrouspotassium carbonate (10.78 g).

TABLE 8 Ex-situ Data Summary for Block Polymers 37-42 Methanol crossoverσ r.t./boiled Water λ IEC [η]₂₅ SW r.t./boiled (mg · mil/ uptake (H₂O/Membrane (meq/g) (dL/g) (%) (S/cm) cc · min · cm²) (%, w/w) H⁺) Example50 1.20 1.09 28 0.020/0.033 0.007/0.026 28 13 Example 51 1.25 0.97 310.024/0.037 0.008/0.017 27 12 Example 52 1.30 0.86 40 0.029/0.0460.011/0.020 28 12 Example 53 1.20 0.89 27 0.021/0.033 0.006/0.019 23 11Example 54 1.25 1.02 29 0.025/0.037 0.008/0.030 25 11 Example 55 1.301.18 33 0.028/0.044 0.008/0.032 27 12

Example 59

OH-ended Oligomer 9: DP=4

This oligomer 9 was synthesized in a similar way as described in theoligomer 17 synthesis, using following compositions: BisK (43.90 g),9,9-bis(4-hydroxyphenyl)fluorene (94.00 g), and anhydrous potassiumcarbonate (48.20 g), 540 mL of DMSO and 270 mL of Toluene.

Example 60

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (9.37 g), SBisK(15.64 g), Oligomer 9 (19.72 g), BisZ (19.32 g), and anhydrous potassiumcarbonate (14.37 g).

Example 61

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (5.04 g), SBisK(15.59 g), Oligomer 9 (29.58 g), BisZ (12.88 g), and anhydrous potassiumcarbonate (10.78 g).

Example 62

This block polymer was synthesized in a similar way as described inExample 13 synthesis, using following compositions: BisK (2.54 g), SBisK(16.22 g), Oligomer 9 (36.97 g), BisZ (9.39 g), and anhydrous potassiumcarbonate (8.98 g).

TABLE 9 Ex-situ Data Summary for Block Polymers 43-45 Methanol crossoverσ r.t./boiled Water λ IEC [η]₂₅ SW r.t./boiled (mg · mil/ uptake (H₂O/Membrane (meq/g) (dL/g) (%) (S/cm) cc · min · cm²) (%, w/w) H⁺) Example60 1.25 0.85 30 0.021/0.032 0.015 25 12 Example 61 1.25 0.53 310.024/0.034 0.022 28 13 Example 62 1.25 0.56 33 0.019/0.029 0.013 26 12

TABLE 10 In-Situ Data Summary for Block Polymers 2, 43-47. Power densityMethanol at 0.4 V crossover HFR Membrane (mW/cm²) (mA/cm²) (Ohm · cm²)Example 2 83 53 0.15 Example 43 87 65 0.20 Example 44 90 96 0.19 Example45 103 31 0.21 Example 46 93 33 0.25 Example 47 73 25 0.24

MEA testing conditions: 3 mg/cm² Pt—Ru in anode, 2 mg/cm² Pt in cathode,60° C. cell temperature, 2.5 stoichiometric air flow, 1M methanol fuel.

The following examples provide further support for the types ofreactions and polymers described throughout this specification.

Example 63

Oligomer 10: DP=4

This oligomer was synthesized in a similar way as described for oligomer10, using following compositions: 4,4′-difluorobenzophone (BisK, 34.91g, 0.16 mol), 9,9-bis(4-hydroxyphenyl)fluorene (42.05 g, 0.12 mol), andanhydrous potassium carbonate (25.87 g, 0.187 mol), 220 mL of DMSO and110 mL of toluene.

This block polymer was synthesized in a similar way as described inExample 1, using following compositions: 4,4′-difluorobenzophone (BisK,7.75 g, 0.0355 mol), 3,3′-disulfonated-4,4′-difluorobenzophone ((SBisK,15.00 g, 0.0355 mol), Oligomer 1 (20.90 g), BisZ (21.47 g, 0.08 mol),and anhydrous potassium carbonate (14.37 g, 0.10 mol), 250 mL of DMSOand 125 mL of toluene. This polymer has an inherent viscosity of 0.49dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80° C.was 52%, cross-over in 8 M methanol was 0.016 mg·mil/cc·min·cm²(non-boiled, conductivity was 0.013 S/cm (non-boiled) and 0.034 S/cm(boiled).

Example 64

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,5.72 g, 0.026 mol), 3,3′-disulfonated-4,4′-difluorobenzophone ((SBisK,17.04 g, 0.040 mol), Oligomer 10 (19.59 g), BisZ (20.12 g, 0.075 mol),and anhydrous potassium carbonate (13.47 g, 0.097 mol), 250 mL of DMSOand 125 mL of Toluene. This polymer has an inherent viscosity of 0.72dl/g in DMAc (0.25 g/dl).

Example 65

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,4.68 g, 0.021 mol), 3,3′-disulfonated-4,4′-difluorobenzophone (SbisK,19.06 g, 0.045 mol), Oligomer 10 (19.59 g),9,9-bis(4-hydroxyphenyl)fluorine (26.28 g, 0.075 mol), and anhydrouspotassium carbonate (13.47 g, 0.097 mol), 250 mL of DMSO and 125 mL ofToluene.

Example 66

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,4.68 g, 0.021 mol), 3,3′-disulfonated-4,4-difluorobenzophone (SBisK,19.06 g, 0.040 mol), Oligomer 10 (19.59 g), bisphenol (13.96 g, 0.075mol), and anhydrous potassium carbonate (13.47 g, 0.075 mol), 250 mL ofDMSO and 125 mL of toluene.

Example 67

This example illustrates block copolymer system using BisK-O block inthe non-ionic region, and SBisK-Z in ionic region, the non-ionic regionconsists of 11%. Size 6 of BisK-O block.

Oligomer 11: DP=6

This oligomer was synthesized in a similar way as described for oligomer10, using following compositions: 4,4′-difluorobenzophone (BisK, 65.46g, 0.30 mol), 4,4′-dihydroxydiphenyl ether (0, 50.55 g, 0.25 mol), andanhydrous potassium carbonate (44.92 g, 0.325 mol), 540 mL of DMSO and270 mL of toluene.

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-diflorobenzophone (BisK,6.51 g, 0.030 mol), 3,3′-disulfonated-4,4-difluorobenzophone (SBisK,17.40 g, 0.041 mol), Oligomer 11 (22.40 g), BisZ (21.47 g, 0.08 mol),and anhydrous potassium carbonate (14.37 g, 0.10 mol), 250 mL of DMSOand 125 mL of toluene.

Example 68

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,4.68 g, 0.021 mol), 3,3′-disulfonated-4,4′-difluorobenzophone (SBisK,19.06 g, 0.040 mol), Oligomer 2 (19.59 g), 1,5-dihydroxynaphthalene(12.01 g, 0.075 mol), and anhydrous potassium carbonate (13.47 g, 0.097mol), 250 mL of DMSO and 125 mL of toluene.

Examples 69-75 illustrate block copolymer system using same BisK-Z innon-ionic region, but sBisK with various aryl phenol groups block havingdifferent chain mobility and chemical affinity in the ionic region. Thenon-ionic block size is 8 and block concentration is 11%.

Example 69 Illustrates Ionic Region Consist of sBisK-Z Unit

Oligomer 12: DP=8

This oligomer 12 was synthesized in a similar way as described inoligomer 1, using following compositions: 4,4′-difluorobenzophone (BisK,65.46 g, 0.3 mol), BisZ (70.44 g, 0.262 mol), and anhydrous potassiumcarbonate (17.97 g, 0.13 mol), 540 mL of anhydrous DMSO (270 mL) oftoluene. This block polymer was synthesized in a similar way asdescribed in example 1, using following compositions:4,4′-difluorobenzophone (BisK, 4.57 g, 0.021 mol),3,3′-disulfonated-4,4′-difluorobenzophone (SBisZ 17.41 g, 0.041 mol),Oligomer 12 (29.72 g), BisZ (18.78 g, 0.07 mol), and anhydrous potassiumcarbonate (12.57 g, 0.091 mol), 270 mL of anhydrous DMSO and 135 mL oftoluene. This polymer has an inherent viscosity of 0.62 dl/g in DMAc(0.25 g/dl).

Example 70 Illustrates Ionic Region Consist of sBisK-FL Unit

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,3.91 g, 0.0179 mol), 3,3′-disulfonated-4,4′-difluorobenzophone (SBisK,14.92 g, 0.06 mol), Oligomer 12 (25.27 g),9,9-bis(4-hydroxyphenyl)fluorene (21.02 g, 0.07 mol), and anhydrouspotassium carbonate (10.78 g, 0.078 mol), 250 mL of DMSO and 125 mL oftoluene. This polymer has an inherent viscosity of 0.84 dl/g in DMAc(0.25 g/dl).

Example 71 Illustrates Ionic Region Consist of sBisK-AF Unit

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,3.91 g, 0.0179 mol), 3,3′-disulfonated-4,4′-difluorobenzophone ((SBisK,14.92 g, 0.035 mol), Oligomer 12 (25.47 g),4,4′-(Hexafluoroisopropylidene)-diphenol (20.17 g, 0.06 mol), andanhydrous potassium carbonate (10.78 g, 0.078 mol), 250 mL of DMSO and125 mL of toluene.

This polymer has an inherent viscosity of 0.47 dl/g in DMAc (0.25 g/dl).

Example 72 Illustrates Ionic Region Consisting of sBisK-B Unit

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,4.57 g, 0.021 mol), 3,3′-disulfonated-4,4′-difluorobenzophone (SBisK,17.41 g, 0.041 mol), Oligomer 12 (29.72 g), 4,4′-dihydroxybiphenyl(13.03 g, 0.07 mol), and anhydrous potassium carbonate (12.57 g, 0.091mol), 250 mL of DMSO and 125 mL of toluene. This polymer has an inherentviscosity of 1.01 dl/g in DMAc (0.25 g/dl).

Example 73 Illustrates Ionic Region Consisting of sBisK-O Unit

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,4.57 g, 0.021 mol), 3,3′-disulfonated-4,4′-difluorobenzophone ((SBisK,17.41 g, 0.041 mol), Oligomer 12 (29.72 g), 4,4′-dihydroxydiphenyl ether(14.15 g, 0.07 mol), and anhydrous potassium carbonate (12.57 g, 0.091mol), 250 mL of DMSO and 125 mL of toluene. This polymer has an inherentviscosity of 0.94 dl/g in DMAc (0.25 g/dl).

Example 74

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,1.298 g, 0.0059 mol), 3,3′-disulfonated-4,4′-difluorobenzophone (SBisK,23.736 g, 0.056 mol), Oligomer 12 (29.72 g), 4,4′-dihydroxydiphenyl(13.03 g, 0.07 mol), and anhydrous potassium carbonate (12.57 g, 0.091mol), 250 mL of DMSO and 125 mL of toluene. This polymer has an inherentviscosity of 1.35 dl/g in DMAc (0.25 g/dl).

Example 75

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,3.91 g, 0.018 mol), 3,3′-disulfonated-4,4′-difluorobenzophone (SBisK,14.92 g, 0.035 mol), Oligomer 12 (25.47 g), 1,5-dihydroxynaphthalene(9.61 g, 0.060 mol), and anhydrous potassium carbonate (10.71 g, 0.078mol), 206 mL of DMSO and 103 mL of Toluene. This polymer has an inherentviscosity of 1.10 dl/g in DMAc (0.25 g/dl).

TABLE 11 summarizes the impact of the chain length and flexible in theionic region on the final membrane properties from Examples 10-16.Cross-over in 8 M Methanol (mg · mil/ Conductivity One-day cc · min ·cm²) (S/cm) (Non- Polymer Swelling (%) (Non-boiled/boiled)boiled/boiled) Example 7 116 0.034/0.081  0.38/0.055 Example 8 460.025/0.020 0.026/0.045 Example 9 141 0.0320/0.11  0.025/0.35  Example10 47 0.036 0.047/0.075 Example 11 155 0.038/0.11  0.059/0.058 Example12 62 0.026/0.046 0.061/0.085 Example 13 94 0.056/0.098 0.10/0.11

Example 76 illustrates block copolymer system using BisK-Z block in thenon-ionic region, and multi components (more than 2 unit) in the ionicregion, in comparison of random copolymer of multi components system.

Example 76

This block polymer was synthesized in a similar way as described inexample 1, using following compositions: 4,4′-difluorobenzophone (BisK,3.91 g, 0.0179 mol), 3,3′-disulfonated-4,4′-difluorobenzophone ((SBisK,14.92 g, 0.035 mol), Oligomer 12 (25.27 g), BisZ (8.05 g, 0.035 mol),9,9-bis(4-hydroxyphenyl)fluorene (10.51 g, 0.035 mol), and anhydrouspotassium carbonate (10.78 g, 0.078 mol), 250 mL of DMSO and 125 mL oftoluene. This polymer has an inherent viscosity of 1.02 dl/g in DMAc(0.25 g/dl). Its one-day swelling in 8 M methanol at 80° C. was 63%,cross-over in 8 M methanol was 0.036 mg·mil/cc·min·cm² (non-boiled) and0.038 mg·mil/cc·min·cm² (boiled), conductivity was 0.026 S/cm(non-boiled) and 0.047 S/cm (boiled).

Example 77

Oligomer 13 (FL4): DP=4

In a 500 mL three necked round flask, equipped with a mechanicalstirrer, a thermometer probe connected with a nitrogen inlet, and aDean-Stark trap/condenser, 4,4′-difluorobenzophone (BisK, 34.91 g, 0.16mol), 9,9-bis(4-hydroxyphenyl)fluorene (42.05 g, 0.12 mol), andanhydrous potassium carbonate (25.87 g, 0.187 mol), 220 mL of DMSO and110 mL of Toluene. The reaction mixture was slowly stirred under a slownitrogen stream. After heating at ˜85° C. for 1 h and at ˜120° C. for 1h, the reaction temperature was raised to ˜135° C. for 3 h, and finallyto ˜170° C. for 2 h. After cooling to ˜70° C. with continuing stirring,the solution was dropped into 1 L of cooled methanol with a vigorousstirring. The precipitates were filtrated and washed with DI-water fourtimes and dried at 80° C. overnight, and then dried at 80° C. undervacuum for 2 days.

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 4.68 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 19.06 g), Oligomer 13(19.59 g), 9,9-bis(4-hydroxyphenyl)fluorene (26.28 g), and anhydrouspotassium carbonate (13.48 g), 240 mL of DMSO and 120 mL of Toluene.This polymer has an inherent viscosity of 1.00 dl/g in DMAc (0.25 g/dl).

Example 78

This block polymer was synthesized in a similar way as described in theoligomer 10 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 4.68 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 19.06 g), Oligomer 10(19.59 g), 4,4′-biphenol (13.97 g), and anhydrous potassium carbonate(13.48 g), 240 mL of DMSO and 120 mL of Toluene. This polymer has aninherent viscosity of 1.89 dl/g in DMAc (0.25 g/dl).

Example 79

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 4.68 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 19.06 g), Oligomer 10(19.59 g), 2,7-dihydroxynaphthalene (12.01 g), and anhydrous potassiumcarbonate (13.48 g), 240 mL of DMSO and 120 mL of Toluene. This polymerhas an inherent viscosity of 1.00 dl/g in DMAc (0.25 g/dl).

Example 80

Oligomer 14 (A8): DP=8

This oligomer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 87.28 g),4,4′-(1,4-phenylenediisopropylidene)bisphenol (79.90 g), and anhydrouspotassium carbonate (62.88 g), 560 mL of DMSO and 280 mL of Toluene.

A block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 1.94 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 7.50 g), Oligomer 14(11.66 g), 9,9-bis(4-hydroxyphenyl)fluorene (10.51 g), and anhydrouspotassium carbonate (5.39 g), 120 mL of DMSO and 60 mL of Toluene. Thispolymer has an inherent viscosity of 0.84 dl/g in DMAc (0.25 g/dl).

Example 81

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 1.94 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 7.50 g), Oligomer 14(11.66 g), 4,4′-biphenol (5.58 g), and anhydrous potassium carbonate(5.39 g), 120 mL of DMSO and 60 mL of Toluene. This polymer has aninherent viscosity of 1.12 dl/g in DMAc (0.25 g/dl).

Example 82

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 1.94 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 7.50 g), Oligomer 14(11.66 g), 1,1-bis(4-hydroxyphenyl)cyclohexane (8.05 g), and anhydrouspotassium carbonate (5.39 g), 120 mL of DMSO and 60 mL of Toluene. Thispolymer has an inherent viscosity of 0.64 dl/g in DMAc (0.25 g/dl).

Example 83

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 0.64 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 11.88 g), Oligomer 14(13.60 g), 9,9-bis(4-hydroxyphenyl)fluorene (12.26 g), and anhydrouspotassium carbonate (6.29 g), 150 mL of DMSO and 75 mL of Toluene. Thispolymer has an inherent viscosity of 0.68 dl/g in DMAc (0.25 g/dl).

Example 84

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 1.94 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 7.50 g), Oligomer 14(11.66 g), 4,4′-(1,4-phenylenediisopropylidene)bisphenol (6.85 g), andanhydrous potassium carbonate (5.39 g), 120 mL of DMSO and 60 mL ofToluene. This polymer has an inherent viscosity of 0.84 dl/g in DMAc(0.25 g/dl).

Example 85

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 2.42 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 9.37 g), Oligomer 14(14.57 g), 2,7-dihydroxynaphthalene (6.00 g), and anhydrous potassiumcarbonate (6.74 g), 120 mL of DMSO and 60 mL of Toluene. This polymerhas an inherent viscosity of 0.97 dl/g in DMAc (0.25 g/dl).

Example 86

Oligomer 15 (AF8): DP=8

This oligomer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 87.28 g),4,4′-(hexafluoroisopropylidene)diphenol (117.69 g), and anhydrouspotassium carbonate (62.88 g), 560 mL of DMSO and 280 mL of Toluene.

Example 87

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 3.88 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 15.00 g), Oligomer 15(29.12 g), 1,1-bis(4-hydroxyphenyl)cyclohexane (16.10 g), and anhydrouspotassium carbonate (10.78 g), 240 mL of DMSO and 120 mL of Toluene.This polymer has an inherent viscosity of 0.72 dl/g in DMAc (0.25 g/dl).

Example 88

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 3.55 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 13.75 g), Oligomer 15(26.70 g), 9,9-bis(4-hydroxyphenyl)fluorene (19.27 g), and anhydrouspotassium carbonate (9.88 g), 240 mL of DMSO and 120 mL of Toluene. Thispolymer has an inherent viscosity of 0.50 dl/g in DMAc (0.25 g/dl).

Example 89

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 4.20 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 16.25 g), Oligomer 15(31.55 g), 4,4′-biphenol (12.10 g), and anhydrous potassium carbonate(11.68 g), 240 mL of DMSO and 120 mL of Toluene. This polymer has aninherent viscosity of 1.29 dl/g in DMAc (0.25 g/dl).

Example 90

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 3.55 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 13.75 g), Oligomer 15(26.70 g), 4,4′-(hexafluoroisopropylidene)diphenol (18.49 g), andanhydrous potassium carbonate (9.88 g), 240 mL of DMSO and 120 mL ofToluene. This polymer has an inherent viscosity of 0.54 dl/g in DMAc(0.25 g/dl).

Example 91

This block polymer was synthesized in a similar way as described in theoligomer 1 synthesis, using following compositions:4,4′-difluorobenzophone (BisK, 4.20 g),3,3′-disulfonated-4,4′-difluorobenzophone (SBisK, 16.25 g), Oligomer 15(31.55 g), 2,7-dihydroxynaphthalene (10.41 g), and anhydrous potassiumcarbonate (11.68 g), 240 mL of DMSO and 120 mL of Toluene. This polymerhas an inherent viscosity of 1.08 dl/g in DMAc (0.25 g/dl).

Synthesis of Regular Block Copolymers

When the preparation of the fluorine-terminated oligomer was complete,the solution was cooled to 120° C., and introduced directly into areaction flask containing the phenoxide-terminated oligomer undernitrogen atmosphere. To obtain the equivalent molar molar ration of aphenoxide end-groups and fluorine end-groups, the phenoxide-terminatedoligomer reaction flask was washed three times with 20 ml DMSO, and thesolution was combined and also poured in the reaction flask. Then thetemperature was again raised to 175-180° C., and maintained there for 6h. The reaction mixture was filtered and a solid precipitated fromacetone or methanol to get the crude product, then washed by hot waterfour times.

Conductivity: 0.046 S/cm, swelling by area in 8M methanol: 88%, 8Mmethanol cross-over: 8.3×10⁻⁷ cm²/sec.

Example 92

Synthesis of Partial Block Polymer with Non-sulfonated HydrophobicSegment

Fluorine end group oligomer 16 preparation (Segment size n=4)

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (80.508), Bis K(87.28 g), anhydrous potassium carbonate (54 g) weredissolved in a mixture DMSO and Toluene (about 20% solid concentration).The mixture was heated to toluene flux with stirring, keeping thetemperature at 140° C. for 4 h, then increase temperature to 175° C. for4 h. The oligomer precipitates from methanol to get the rude product,then washed by hot water four times. Dry at 80° C. oven for one day and75° C. vacuum oven for 2 days.

Polymerization

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (13.418),Bis K(4.8878 g), S-Bis K(9.2884 g), oligomer 16 (11.2112 g),anhydrous potassium carbonate (9.0 g) were dissolved in a mixture DMSOand Toluene (about 20% solid concentration). The mixture was heated totoluene flux with stirring, keeping the temperature at 140° C. for 6 h,then increase temperature to 173-175° C. for 4-4.5 h. The reactionmixture precipitates from methanol to get the crude product.

Conductivity: 0.015 S/cm, Swelling by area in 8M methanol solution: 51%,8M

Methanol Cross-over: 3.5×10⁻⁷ cm²/sec.

Example 93

Synthesis of Partial Block Polymer with Non-sulfonated HydrophobicSegment

Fluorine end group oligomer 17 (BisZ/BisK) preparation (segment sizen=4)

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (80.508), Bis K(87.28 g), anhydrous potassium carbonate (54 g) weredissolved in a mixture DMSO and Toluene (about 20% solid concentration).The mixture was heated to toluene flux with stirring, keeping thetemperature at 140° C. for 4 h, then increase temperature to 175° C. for4 h. The reaction mixture precipitates from methanol to get the rudeproduct, and then washed by hot water four times. Dry at 80 C oven forone day and 75 C vacuum oven for 2 days.

Polymerization

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (13.418), BisK(5.2368 g), S-Bis K (8.4444 g), oligomer 17 (12.0112 g,n=4, fluorine end of BisZ/BisK composition), anhydrous potassiumcarbonate (9.0 g) were dissolved in a mixture DMSO and Toluene (about20% solid concentration). The mixture was heated to toluene flux withstirring, keeping the temperature at 140° C. for 6 h, then increasetemperature to 173-175° C. for 4-4.5 h. The reaction mixtureprecipitates from methanol to get the rude product.

Conductivity: 0.014 S/cm (0.038 S/cm, boiled), swelling by area in 8Mmethanol: 60%, 8M methanol cross-over: 0.019 mg/min·ml·mls.

Example 94

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (13.418), BisK (4.8878 g), S-Bis K(9.2884 g), oligomer 17 (11.2112 g,n=4, fluorine end of BisZ/BisK composition), anhydrous potassiumcarbonate (9.0 g) were dissolved in a mixture DMSO and Toluene (about20% solid concentration). The mixture was heated to toluene flux withstirring, keeping the temperature at 140° C. for 6 h, then increasetemperature to 173-175° C. for 4-4.5 h. The reaction mixtureprecipitates from methanol to get the rude product.

Conductivity: 0.0146 S/cm (0.0378 S/cm, boiled), swelling by area in 8Mmethanol: 51%, 8M methanol cross-over: 0.022 mg/min·ml·mls.

Example 95

Synthesis of Partial Block Polymer with Non-sulfonated HydrophobicSegment

Fluorine end group oligomer 18 preparation (segment size n=6)

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (89.4533 g), 4,4′-difluorobenzophone (Bis K, 87.28 g), anhydrouspotassium carbonate (54 g) were dissolved in a mixture DMSO and Toluene(about 20% solid concentration). The mixture was heated to toluene fluxwith stirring, keeping the temperature at 140° C. for 4 h, then increasetemperature to 175° C. for 4 h. The reaction mixture precipitates frommethanol to get the rude product, and then washed by hot water fourtimes. Dry at 80 C oven for one day and 75 C vacuum oven for 2 days.

Polymerization

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (13.418), Bis K(4.8878 g), 3,3′-disulfonated-4,4′-difluorobenzophone(S-Bis K, 8.444 g), oligomer(9.953 g, n=6, fluorine end of BisZ/BisKcomposition), anhydrous potassium carbonate (9.0 g) were dissolved in amixture DMSO and Toluene (about 20% solid concentration). The mixturewas heated to toluene flux with stirring, keeping the temperature at140° C. for 6 h, then increase temperature to 173-175° C. for 4-4.5 h.The reaction mixture precipitates from methanol to get the rude product.

Example 96

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-Biphenol (9.3105), Bis K(4.8878 g), S-Bis K(9.2884 g), oligomer 18(11.2112 g, n=4, fluorine end of BisZ/BisK composition), anhydrouspotassium carbonate (9.0 g) were dissolved in a mixture DMSO and Toluene(about 20% solid concentration). The mixture was heated to toluene fluxwith stirring, keeping the temperature at 140° C. for 6 h, then increasetemperature to 173-175° C. for 4-4.5 h. The reaction mixtureprecipitates from methanol to get the rude product.

Conductivity: 0.012 S/cm(0.0211 S/cm, boiled), swelling by area in 8Mmethanol: 21%,

Example 97

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-Biphenol (8.3794 g), Bis K(1.2444 g), S-Bis K(12.9794 g), oligomer18 (18.00 g, n=4, fluorine end of BisZ/BisK composition), anhydrouspotassium carbonate (9.0 g) were dissolved in a mixture DMSO and Toluene(about 20% solid concentration). The mixture was heated to toluene fluxwith stirring, keeping the temperature at 140° C. for 6 h, then increasetemperature to 173-175° C. for 4-4.5 h. The reaction mixtureprecipitates from methanol to get the rude product.

Conductivity: 0.0427 S/cm(0.078 S/cm, boiled), swelling by area in 8Mmethanol: 61%, 8M methanol cross-over: 0.052 mg/min·ml·mls.

Example 98

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-Biphenol (8.3794 g), Bis K(1.1032 g), S-Bis K(13.6625 g), oligomer18 (15.1777 g, n=4, fluorine end of BisZ/BisK composition), anhydrouspotassium carbonate (9.0 g) were dissolved in a mixture DMSO and Toluene(about 20% solid concentration). The mixture was heated to toluene fluxwith stirring, keeping the temperature at 140° C. for 6 h, then increasetemperature to 173-175° C. for 4-4.5 h. The reaction mixtureprecipitates from methanol to get the rude product.

Conductivity: 0.067 S/cm(0.096 S/cm, boiled), swelling by area in 8Mmethanol: 72%, 8M methanol cross-over: 0.06 mg/min·ml·mls.

Example 99

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-Biphenol (8.3794), Bis K(0.3078 g), S-Bis K(15.0287 g), oligomer 18(16.0714 g, n=4, fluorine end of BisZ/BisK composition), anhydrouspotassium carbonate (9.0 g) were dissolved in a mixture DMSO and Toluene(about 20% solid concentration). The mixture was heated to toluene fluxwith stirring, keeping the temperature at 140° C. for 6 h, then increasetemperature to 173-175° C. for 4-4.5 h. The reaction mixtureprecipitates from methanol to get the rude product.

Conductivity: 0.072 S/cm(0.0922 S/cm, boiled), swelling by area in 8Mmethanol: 98%, 8M methanol cross-over: 0.067 mg/min·ml·mls.

Example 100

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-(Hexafluoroisopropylidene)-diphenol (6F, 16.8065 g), Bis K(4.8878g), S-Bis K(9.2884 g), oligomer 18 (11.2112 g, n=4, fluorine end ofBisZ/BisK composition), anhydrous potassium carbonate (9.0 g) weredissolved in a mixture DMSO and Toluene (about 20% solid concentration).The mixture was heated to toluene flux with stirring, keeping thetemperature at 140° C. for 6 h, then increase temperature to 173-175° C.for 4-4.5 h. The reaction mixture precipitates from methanol to get therude product.

Conductivity: 0.007 S/cm(0.0122 S/cm, boiled), swelling by area in 8Mmethanol: 24%, 8M methanol cross-over: 0.016 mg/min·ml·mls.

Example 101

Synthesis of Partial Block Polymer with Non-Sulfonated HydrophobicSegment

Fluorine end group oligomer 19 (6F/BisK) preparation (segment size n=4)

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-(Hexafluoroisopropylidene)-diphenol (6F, 100.839 g), Bis K(87.28g), anhydrous potassium carbonate (54 g) were dissolved in a mixtureDMSO and Toluene (about 20% solid concentration). The mixture was heatedto toluene flux with stirring, keeping the temperature at 140° C. for 4h, then increase temperature to 175° C. for 4 h. The reaction mixtureprecipitates from methanol to get the rude product, and then washed byhot water four times. Dry at 80 C oven for one day and 75 C vacuum ovenfor 2 days

Polymerization

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (13.418), Bis K(4.8878 g), S-Bis K(9.2884 g), oligomer 19 (12.7333 g,n=4, fluorine end of 6F/BisK composition), anhydrous potassium carbonate(9.0 g) were dissolved in a mixture DMSO and Toluene (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture precipitates from methanolto get the rude product.

Conductivity: 0.0114 S/cm(0.6321 S/cm, boiled), swelling by area in 8Mmethanol: 38%, 8M methanol cross-over: 0.013 mg/min·ml·mls.

Example 102

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′-(1,4-phenyldiisopropyldiene)bisphenol (17.30 g), Bis K(4.8878 g),S-Bis K(9.2884 g), oligomer 19 (12.733 g, n=4, fluorine end of 6F/BisKcomposition), anhydrous potassium carbonate (9.0 g) were dissolved in amixture DMSO and Toluene (about 20% solid concentration). The mixturewas heated to toluene flux with stirring, keeping the temperature at140° C. for 6 h, then increase temperature to 173-175° C. for 4-4.5 h.The reaction mixture precipitates from methanol to get the rude product.

Conductivity: 0.0102 S/cm(0.0215 S/cm, boiled), swelling by area in 8Mmethanol: 37%

Example 103

Synthesis of Partial Block Polymer with Non-sulfonated HydrophobicSegment

Fluorine end group oligomer 20 (6F/BisK) preparation (segment size n=8)

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser,4,4′(Hexafluoroisopropylidene)-diphenol (6F, 117.6455 g), Bis K(87.28g), anhydrous potassium carbonate (54 g) were dissolved in a mixtureDMSO and Toluene (about 20% solid concentration). The mixture was heatedto toluene flux with stirring, keeping the temperature at 140° C. for 4h, then increase temperature to 175° C. for 4 h. The reaction mixtureprecipitates from methanol to get the rude product, and then washed byhot water four times. Dry at 80 C oven for one day and 75 C vacuum ovenfor 2 days

Polymerization

In a 500 ml three necked round flask, equipped with a mechanicalstirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, BisZ (13.418), Bis K(3.2729 g), S-Bis K(12.4151 g), oligomer 20 (24.2454 g,n=8, fluorine end of 6F/BisK composition), anhydrous potassium carbonate(9.0 g) were dissolved in a mixture DMSO and Toluene (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture precipitates from methanolto get the rude product.

Conductivity: 0.011 S/cm(0.0211 S/cm, boiled), swelling by area in 8Mmethanol: 37%, 8M methanol cross-over: 0.023 mg/min·ml·mls.

Example 104

Following Examples Demonstrate the Effect of Various Block Size andSulfonation degree

Oligomer 21 Preparation (Block size n=4)

In a 2 L three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (80.508), Bis K(87.28 g), anhydrouspotassium carbonate (71.86 g) were dissolved in a mixture DMSO andtoluene, 720 ml and 360 ml respectively (about 20% solid concentration).The mixture was heated to toluene reflux with stirring, keeping thetemperature at 140° C. for 4 h, then increasing the temperature to 175°C. for 4 h. The reaction mixture was precipitated into 2 L of methanolto get the crude product; then washed with hot DI water four times. Theproduct was oven dried at 80° C. for one day and vacuum dried at 75° C.for 2 days.

Polymerization

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (13.418), Bis K(4.8878 g), S-Bis Ksodium salt (9.2902 g), oligomer 21 (n=4) (11.2112 g), anhydrouspotassium carbonate (17.9 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Theproduct was oven dried at 80 C for one day and vacuum dried at 75 C for2 days. The dried sample (0.1250 g) was in 25 ml of dimethylacetamide(DMAc) to determine inherent viscosity. The inherent viscosity of thesodium salt polymer was found to be 0.67 dL/g. A sample was prepared forGPC analysis by dissolving 50 mg of polymer in 20 ml of DMAc containing0.1M LiBr. The sample was found to have a peak molecular weight of about46, 350 based upon polystyrene standards.

Example 105

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (13.418), Bis K(6.0441 g), S-Bis Ksodium salt (7.0521 g), oligomer 21 (n=4) (17.2480 g), anhydrouspotassium carbonate (17.9 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Theproduct was oven dried at 80 C for one day and vacuum dried at 75 C for2 days. The dried sample (0.1250 g) was in 25 ml of dimethylacetamide(DMAc) to determine inherent viscosity. The inherent viscosity of thesodium salt polymer was found to be 0.49 dL/g.

Example 106

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (13.418 g), Bis K(3.8621 g), S-Bis Ksodium salt (11.2750 g), oligomer 21 (n=4) (17.2481 g), anhydrouspotassium carbonate (17.9 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Theproduct was oven dried at 80 C for one day and vacuum dried at 75 C for2 days. The dried sample (0.1250 g) was in 25 ml of dimethylacetamide(DMAc) to determine inherent viscosity. The inherent viscosity of thesodium salt polymer was found to be 0.643 dL/g.

Example 107

Oligomer 22 Preparation (Block Size n=8)

In a 2 L three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (70.4445 g), Bis K(65.4600 g),anhydrous potassium carbonate (47.1912 g) were dissolved in a mixtureDMSO and toluene, 540 ml and 270 ml respectively (about 20% solidconcentration). The mixture was heated to toluene reflux with stirring,keeping the temperature at 140° C. for 4 h, then increasing thetemperature to 175° C. for 4 h. The reaction mixture was precipitatedinto 2 L of methanol to get the crude product; then washed with hot DIwater four times. The product was oven dried at 80 C for one day andvacuum dried at 75 C for 2 days.

Polymerization

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (13.4180 g), Bis K(3.2729 g), S-Bis Ksodium salt (12.4151 g), oligomer 22 (n=8) (21.2299 g), anhydrouspotassium carbonate (17.9 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Theproduct was oven dried at 80 C for one day and vacuum dried at 75 C for2 days. The dried sample (0.1250 g) was in 25 ml of dimethylacetamide(DMAc) to determine inherent viscosity. The inherent viscosity of thesodium salt polymer was found to be 0.90 dL/g.

Example 108

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (13.4180 g), Bis K(4.8223 g), S-Bis Ksodium salt (9.4169 g), oligomer 22 (n=8) (21.2296 g), anhydrouspotassium carbonate (17.9 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Theproduct was oven dried at 80° C. for one day and vacuum dried at 75° C.for 2 days. The dried sample (0.1250 g) was in 25 ml ofdimethylacetamide (DMAc) to determine inherent viscosity. The inherentviscosity of the sodium salt polymer was found to be 0.935 dl/g. Asample was prepared for GPC analysis by dissolving 50 mg of polymer in20 ml of DMAc containing 0.1M LiBr. The sample was found to have a peakmolecular weight of about 106,040 based upon polystyrene standards.

Example 109

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (13.4180 g), Bis K(1.8984 g), S-Bis Ksodium salt (15.0757 g), oligomer 22 (n=8) (21.2296 g), anhydrouspotassium carbonate (17.9 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Theproduct was oven dried at 80° C. for one day and vacuum dried at 75° C.for 2 days. The dried sample (0.1250 g) was in 25 ml ofdimethylacetamide (DMAc) to determine inherent viscosity. The inherentviscosity of the sodium salt polymer was found to be 0.992 dL/g.

Example 110

Oligomer 23 Preparation (Block Size n=2)

In a 2 L three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (53.6721 g), Bis K(87.2800 g),anhydrous potassium carbonate (71.8692 g) were dissolved in a mixtureDMSO and toluene, 750 ml and 360 ml respectively (about 20% solidconcentration). The mixture was heated to toluene reflux with stirring,keeping the temperature at 140° C. for 4 h, then increasing thetemperature to 175° C. for 4 h. The reaction mixture was precipitatedinto 2 L of methanol to get the crude product; then washed with hot DIwater four times. The product was oven dried at 80° C. for one day andvacuum dried at 75° C. for 2 days.

Example 111

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (20.1270 g), Bis K(8.5424 g), S-Bis Ksodium salt (11.5917 g), oligomer 23 (n=2) (6.2215), anhydrous potassiumcarbonate (17.9 g) were dissolved in a mixture dimethylsulfoxide (DMSO)(190 ml) and toluene (100 ml) (about 20% solid concentration). Themixture was heated to toluene flux with stirring, keeping thetemperature at 140° C. for 6 h, then increase temperature to 173-175° C.for 4-4.5 h. The reaction mixture was precipitated into 2 L of methanol.The polymer was then washed with DI water 4 times. The product was ovendried at 80 C for one day and vacuum dried at 75 C for 2 days. The driedsample (0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determineinherent viscosity. The inherent viscosity of the sodium salt polymerwas found to be 0.466 dL/g.

Example 112

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (20.1270 g), Bis K(9.9827 g), S-Bis Ksodium salt (8.8046 g), oligomer 23 (n=2) (6.2214 g), anhydrouspotassium carbonate (27.0629 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Theproduct was oven dried at 80 C for one day and vacuum dried at 75 C for2 days.

Example 113

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (20.1270 g), Bis K(7.2661), S-Bis Ksodium salt (14.0620 g), oligomer 23 (n=2) (6.2217 g), anhydrouspotassium carbonate (13.4759 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (180 ml) and toluene (90 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times.

Example 114

Oligomer 24 Preparation (Block Size n=12) In a 1 L three necked roundbottom flask, equipped with a mechanical stirrer, thermocouple, heatingmantle, controller, nitrogen inlet and Dean-Stark trap/condenser, Bis Z(73.7990 g), Bis K(65.4600 g), anhydrous potassium carbonate (53.9019 g)were dissolved in a mixture DMSO and toluene, 540 ml and 270 mlrespectively (about 20% solid concentration). The mixture was heated totoluene reflux with stirring, keeping the temperature at 140° C. for 4h, then increasing the temperature to 175° C. for 4 h. The reactionmixture was precipitated into 2 L of methanol to get the crude product;then washed with hot DI water four times. The product was oven dried at80 C for one day and vacuum dried at 75 C for 2 days.

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (20.1270 g), S-Bis K sodium salt(28.1240 g), oligomer 24 (n=12) (31.2316 g), anhydrous potassiumcarbonate (13.5589 g) were dissolved in a mixture dimethylsulfoxide(DMSO) (300 ml) and toluene (100 ml) (about 20% solid concentration).The mixture was heated to toluene flux with stirring, keeping thetemperature at 140° C. for 6 h, then increase temperature to 173-175° C.for 4-4.5 h. The reaction mixture was precipitated into 2 L of methanol.The polymer was then washed with DI water 4 times. The dried sample(0.1250 g) was in 25 ml of dimethylacetamide (DMAc) to determineinherent viscosity. The inherent viscosity of the sodium salt polymerwas found to be 0.490 dL/g.

Example 115

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (16.1017 g), Bis K (6.3366 g), S-Bis Ksodium salt (11.6552 g), oligomer 24 (n=8) (12.7379 g), anhydrouspotassium carbonate (10.7841 g) were dissolved in a mixturedimethylsulfoxide (DMSO) (200 ml) and toluene (100 ml) (about 20% solidconcentration). The mixture was heated to toluene flux with stirring,keeping the temperature at 140° C. for 6 h, then increase temperature to173-175° C. for 4-4.5 h. The reaction mixture was precipitated into 2 Lof methanol. The polymer was then washed with DI water 4 times. Thepolymer was found to have an inherent viscosity of 0.66 dL/g in theproton form.

Example 116

In a 500 ml three necked round bottom flask, equipped with a mechanicalstirrer, thermocouple, heating mantle, controller, nitrogen inlet andDean-Stark trap/condenser, Bis Z (13.4180 g), S-Bis K sodium salt(17.5670 g), oligomer 24 (n=8) (31.8444 g), anhydrous potassiumcarbonate (8.9837 g) were dissolved in a mixture dimethylsulfoxide(DMSO) (250 ml) and toluene (125 ml) (about 20% solid concentration).The mixture was heated to toluene flux with stirring, keeping thetemperature at 140° C. for 6 h, then increase temperature to 173-175° C.for 4-4.5 h. The reaction mixture was precipitated into 2 L of methanol.The polymer was then washed with DI water 4 times. The polymer was foundto have an inherent viscosity of 0.83 dL/g in the proton form.

1. An ion conductive copolymer having the formula:—((Ar₁—X₁—Ar₂—X₂—Ar₃—X₃)_(m)—Ar₁—X₁—Ar₂—)_(a)/((Ar₄—X₄—Ar₅—X₅—Ar₆—X₆)_(n)—Ar₄—X₄—Ar₅—)_(b)/(—Ar₇—X₇—Ar₈—)_(c)R₁—Ar₉—Y—Ar₁₀—R₂—where —((Ar₁—X₁—Ar₂—X₂—Ar₃—X₃)_(m)—Ar₁—X₁—Ar₂—)_(a) and((Ar₄—X₄—Ar₅—X₅—Ar₆—X₆)_(n)—Ar₄—X₄—Ar₅—) are different hydrophobicoligomers, where Ar₁, Ar₂, Ar₄, Ar₅, Ar₇, Ar₈, Ar₉ and Ar₁₀ areindependently phenyl, substituted phenyl napthyl, terphenyl, arylnitrile, substituted aryl nitrile, and Ar₇ and/or Ar₈ further comprisean ion conducting group, X₁ and X₄ are independently —C(O)— or —S(O)₂,X₂, X₃, X₅ and X₆ are independently —O— or —S—; X₇ is a bond, —C(O)— orS(O)₂—, Ar₃ and Ar₆ are the same or different from each other and are

and wherein the ion conductive groups comprise SO₃ ⁻, —COO⁻, H₂PO₃ ⁻ orsulfonimide; R₁ and R₂ are independently —O— or —S—, wherein a, b and care independently between 0.01 and 0.98 and a+b+c=1, wherein m isbetween 1 and 12, n is between 1 and 12, and wherein Y is a bond,—C(O)—, —S(O₂)—, and Ar₁₀ may be present or absent when Y is a bond. 2.An ion conducting copolymer having the formula:(Ar₃—X₃—Ar₁—X₁Ar₂—X₂)_(m)—Ar₃—)_(a)/(Ar₆—X₆—Ar₄—X₄—Ar₅—X₅)_(n)—Ar₆—)_(b)/(Ar₇—X₇−Ar₈)_(c)—R₁—Ar₉—Y—Ar₁₀—R₂where (Ar₃—X₃—Ar₁—X₁Ar₂—X₂)_(m)—Ar₃— and (Ar₆—X₆—Ar₄—X₄—Ar₅—X₅)—Ar₆ aredifferent hydrophobic oligomers, where Ar₁, Ar₂ Ar₄, Ar₅, Ar₇, Ar₈, Ar₉and Ar₁₀ are independently phenyl, substituted phenyl napthyl,terphenyl, aryl nitrile, substituted aryl nitrile, and Ar₇ and/or Ar₈further comprise an ion conducting group, X₁ and X₄ are independently—C(O)— or —S(O)₂, X₂, X₃, X₅ and X₆ are independently —O— or —S—; X₇ isa bond, —C(O)— or S(O)₂—, Ar₃ and Ar₆ are the same or different fromeach other and are

wherein the ion conductive group comprises —SO₃H, —COOH, —HPO₃H or—SO₂NH—SO₂—RF where RF is a perfluorinated hydrocarbon having 1-20carbon atoms and said ion conducting group are pendant to the copolymerbackbone; R₁ and R₂ are independently —O— or —S—, wherein a, b and c areindependently between 0.01 and 0.98 and a+b+c=1, wherein m is between 1and 10, and wherein Y is a bond, —C(O)—, —S(O₂)—, and Ar₁₀ may bepresent or absent when Y is a bond.
 3. An ion conductive copolymerhaving the formula(Ar₃—X₃—Ar₁—X₁Ar₂—X₂)_(m)—Ar₃—)_(a)/(Ar₆—X₆—Ar₄—X₄—Ar₅—X₅)_(n)—Ar₆—)/(Ar₇—X₇.Ar₈)_(c)—R₁—Ar₉—Y—Ar₁₀—R₂ where Ar₁, Ar₂, Ar₄, Ar₅, Ar₇, Ar₈, Ar₉ andAr₁₀ are independently phenyl, substituted phenyl napthyl, terphenyl,aryl nitrile, substituted aryl nitrile, and Ar₇ and/or Ar₈ furthercomprise an ion conducting group, X₁ and X₄ are independently —C(O)— or—S(O)₂, X₂, X₃, X₅ and X₆ are independently —O— or —S—; X₇ is a bond,—C(O)— or S(O)₂—, where the Ar₃ monomers are the same or different fromeach other and are

where the Ar₆ monomers are the same or different from each other and are

wherein the ion conductive group comprises —SO₃H, —COOH, —HPO₃H or—SO₂NH—SO₂—RF where RF is a perfluorinated hydrocarbon having 1-20carbon atoms and said ion conducting group are pendant to the copolymerbackbone; R₁ and R₂ are independently —O— or —S—, wherein a, b and c areindependently between 0.01 and 0.98 and a+b+c=1, wherein m is between 1and 12, n is between 1 and 12, and wherein Y is a bond, —C(O)—, —S(O₂)—,and Ar₁₀ may be present or absent when Y is a bond.
 4. An ion conductivecopolymer having the formula:

wherein Ar is:

and wherein a is between 0.05 and 0.2, b is between 0.01 and 0.2 and cis between 0.5 and 0.95.
 5. An ion conductive copolymer having theformula


6. An ion conducting copolymer having the formula